TWI912798B - Substrate processing method and substrate processing apparatus, and semiconductor device manufacturing method and semiconductor manufacturing apparatus - Google Patents

Abstract

This invention provides a substrate processing method and apparatus for efficiently forming a dense and protective autologous monolayer on a substrate surface in a short time by suppressing or reducing the generation of film defects, as well as a semiconductor device manufacturing method and semiconductor manufacturing apparatus. The substrate processing method of the present invention forms SAM on the surface Wf of substrate W, and includes: a surface modification step S102, which involves attaching hydroxyl groups to the surface Wf of substrate W to perform surface modification; and a film formation step S104, which involves contacting a processing liquid containing SAM molecules capable of forming SAM with the surface Wf of substrate W after surface modification step S102 to form SAM. The molecules have hydroxyl groups. The film formation step S104 is as follows: through the dehydration condensation reaction between the hydroxyl groups attached to the surface Wf of substrate W and the hydroxyl groups of SAM molecules, SAM molecules are chemically adsorbed onto the surface Wf of substrate W to form SAM.

Description

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

This invention relates to a substrate processing method and apparatus capable of efficiently forming autotissued monolayers with excellent density and protective properties in a short time, as well as a semiconductor device manufacturing method and semiconductor manufacturing apparatus.

In the manufacturing of semiconductor devices, photolithography is widely used as a technique for selectively forming films on specific surface areas of a substrate. For example, after the formation of the underlying wiring, an insulating film is formed, and a double-layer metal inlay structure with trenches and vias is formed by photolithography and etching. Conductive films such as Cu are embedded in the trenches and vias to form wiring.

However, in recent years, semiconductor devices have become increasingly miniaturized, and the alignment accuracy of photolithography is sometimes insufficient. Therefore, there is a need for a method that can selectively form films on specific areas of the substrate surface with high precision to replace photolithography.

For example, Patent Document 1 discloses a method for selectively etching a silicon nitride (SiN) film and a silicon oxide ( _SiO2 ) film on a substrate in which a heat-resistant phosphoric acid material is pre-formed as SAM on the surface of the silicon oxide film.

Here, to fully protect the silicon oxide film from the effects of the etching solution, it is necessary to form a highly dense SAM (Silicon Aluminum Metallized Atomizer). However, previous SAM deposition methods suffer from the problem of difficulty in forming such a dense SAM within a short time, resulting in poor production efficiency. [Prior Art Documents] [Patent Documents]

[Patent Document 1] Japanese Patent No. 5490071

[The problem that the invention aims to solve]

This invention addresses the aforementioned problems and aims to provide a substrate processing method and apparatus for efficiently forming a dense and protective autologous monolayer on a substrate surface in a short time by suppressing or reducing the generation of film defects; as well as a semiconductor device manufacturing method and apparatus. [Technical Means for Solving the Problems]

To address the aforementioned issues, the substrate processing method of this invention is characterized by forming a self-tissued monomolecular film on the surface of a substrate. This method includes: a surface modification step, which involves applying hydroxyl groups to the surface of the substrate to perform surface modification; and a film formation step, which involves contacting a processing liquid containing molecules capable of forming the self-tissued monomolecular film onto the surface of the substrate after the surface modification step to form the self-tissued monomolecular film. The molecules have functional groups capable of undergoing dehydration condensation reactions with the hydroxyl groups. The film formation step involves the following steps: through the dehydration condensation reaction between the hydroxyl groups and the functional groups of the molecules, the molecules are chemically adsorbed onto the surface of the substrate.

In the film formation step of the above configuration, molecules (hereinafter, sometimes referred to as "SAM molecules") capable of forming self-tissued monolayers (SAMs) are chemically adsorbed onto the surface of the substrate, thereby forming SAMs. However, in the SAMs formed during the film formation step, there are instances where SAM molecules fail to chemically adsorb onto the substrate surface, resulting in film defects. Especially when the contact time between the SAM molecules and the substrate surface is short, the frequency of in-plane film defects increases, or the area of film defects becomes larger. However, in the above configuration, a surface modification step of applying hydroxyl groups to the substrate surface is performed before the film formation step. Therefore, if SAM molecules with functional groups capable of dehydration condensation reactions with hydroxyl groups come into contact with the substrate surface, a dehydration condensation reaction occurs between the functional groups of the SAM molecules and the hydroxyl groups on the substrate surface, allowing the SAM molecules to be chemically adsorbed onto the substrate surface at a high density. As a result, even if the previous substrate treatment method is not as effective, allowing SAM molecules to remain in contact with the substrate surface for a longer period of time to form dense SAM can suppress the formation of film defects and efficiently form SAM with excellent density and protective properties in a short period of time.

In the above configuration, the surface modification step can also be a step of contacting the surface modification liquid containing an alkaline solution to the surface of the substrate. By contacting the alkaline solution to the surface of the substrate, more hydroxyl groups can be imparted to the surface of the substrate. As a result, more SAM molecules can be chemically adsorbed onto the surface of the substrate, thereby forming SAM with excellent density and protective properties.

Furthermore, in the above-described configuration, the alkaline solution is preferably an ammonia-hydrogen peroxide mixture, ammonia water, tetramethylammonium hydroxide aqueous solution, or trimethyl-2-hydroxyethylammonium hydroxide aqueous solution.

Furthermore, in the above configuration, the surface modification step can also involve irradiating the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms. This allows for the deposition of more hydroxyl groups onto the substrate surface. As a result, more SAM molecules can be chemically adsorbed onto the substrate surface, forming SAM with excellent density and protective properties.

Furthermore, in the above configuration, it is preferable to include a pretreatment step before the surface modification step, in which a pretreatment solution containing hydrogen fluoride is brought into contact with the surface of the substrate. This allows for effective introduction of hydroxyl groups during the surface modification step. As a result, SAM molecules can be chemically adsorbed onto the substrate surface at a further high density, forming SAM with even superior density and protective properties.

To address the aforementioned problems, the present invention provides a method for manufacturing a semiconductor device characterized by: processing a substrate on which a laminate is disposed on its surface, wherein the laminate comprises alternating layers of a protected layer (which serves as the object of etching) and an etched layer (which serves as the object of etching); the method for manufacturing the semiconductor device includes: a step of selectively forming an autologous monolayer on at least the surface of the protected layer; and a step of selectively etching the etched layer using the autologous monolayer as a protective layer; the step of forming the autologous monolayer includes... The process includes a surface modification step, which involves applying hydroxyl groups to the surface of the protected layer to modify its surface; and a film formation step, which involves contacting a treatment solution containing molecules capable of forming the self-tissued monolayer with the surface modification step on the surface of the protected layer to form the self-tissued monolayer. The molecules have functional groups capable of undergoing dehydration condensation reactions with the hydroxyl groups. The film formation step is as follows: the molecules are chemically adsorbed onto the surface of the protected layer by the dehydration condensation reaction between the hydroxyl groups and the functional groups of the molecules.

In the film formation step of the above configuration, SAM molecules are formed by self-organization through chemical adsorption onto the surface of the protected layer. However, in the SAM formed during the film formation step, there are instances where SAM molecules fail to chemically adsorb onto the surface of the protected layer, resulting in film defects. Especially when the contact time between SAM molecules and the surface of the protected layer is short, the frequency of in-plane film defects increases, or the area of film defects becomes larger. However, in the above configuration, a surface modification step of applying hydroxyl groups to the surface of the protected layer is performed before the film formation step. Therefore, if SAM molecules with functional groups capable of dehydration condensation reactions with hydroxyl groups come into contact with the surface of the protected layer, a dehydration condensation reaction occurs between the functional groups of the SAM molecules and the hydroxyl groups on the surface of the protected layer, allowing the SAM molecules to be chemically adsorbed onto the surface of the protected layer at a high density. As a result, even if it is not as advanced as the previous semiconductor device manufacturing methods, allowing SAM molecules to remain in contact with the surface of the protected layer for a long time in order to form a dense SAM can suppress the generation of film defects and efficiently form a dense SAM with excellent protective properties in a short time.

In the above configuration, the surface modification step can also be a step of contacting the surface modification liquid containing an alkaline solution with the surface of the protected layer. By contacting the alkaline solution with the surface of the protected layer, more hydroxyl groups can be imparted to the surface of the protected layer. As a result, more SAM molecules can be chemically adsorbed onto the surface of the protected layer, forming SAM with excellent density and protective properties.

Furthermore, in the above-described configuration, the alkaline solution is preferably an ammonia-hydrogen peroxide mixture, ammonia water, tetramethylammonium hydroxide aqueous solution, or trimethyl-2-hydroxyethylammonium hydroxide aqueous solution.

Furthermore, in the above configuration, the surface modification step can also be a step of irradiating the surface of the protected layer with ultraviolet light in an atmosphere containing oxygen atoms. This allows for the application of more hydroxyl groups to the surface of the protected layer. As a result, more SAM molecules can be chemically adsorbed onto the surface of the protected layer, forming a SAM with excellent density and protective properties.

Furthermore, in the above configuration, it is preferable to include a pretreatment step before the surface modification step, in which a pretreatment solution containing hydrogen fluoride is brought into contact with the surface of the protected layer. This allows for effective introduction of hydroxyl groups during the surface modification step. As a result, SAM molecules can be chemically adsorbed onto the surface of the protected layer at a further high density, forming SAM with even superior density and protective properties.

To solve the above problems, the substrate processing apparatus of the present invention is characterized in that it is a substrate processing apparatus for forming a self-tissued monomolecular film on the surface of a substrate, and includes: a surface modification section, which performs surface modification by applying hydroxyl groups to the surface of the substrate; and a processing liquid supply section, which supplies the surface-modified substrate surface with a processing liquid containing molecules capable of forming the self-tissued monomolecular film, thereby forming the self-tissued monomolecular film. The molecules have functional groups capable of undergoing dehydration condensation reactions with the hydroxyl groups. The processing liquid supply section chemically adsorbs the molecules onto the surface of the substrate by means of the dehydration condensation reaction between the hydroxyl groups and the functional groups of the molecules.

According to the above structure, the surface modification section performs surface modification on the substrate surface by imparting hydroxyl groups to the substrate surface. Furthermore, the treatment liquid supply section forms SAM by bringing a treatment liquid containing SAM molecules into contact with the substrate surface. Here, SAM molecules have functional groups capable of dehydration condensation reactions with hydroxyl groups. Therefore, when SAM molecules contact the substrate surface, a dehydration condensation reaction occurs between the functional groups of the SAM molecules and the hydroxyl groups on the substrate surface, allowing SAM molecules to be chemically adsorbed onto the substrate surface. Furthermore, the chemically adsorbed SAM molecules undergo self-organization, thereby forming SAM. However, in the SAM formed on the substrate surface, there are instances where SAM molecules cannot be chemically adsorbed onto the substrate surface, resulting in film defects. Especially when the contact time between SAM molecules and the substrate surface is short, the frequency of in-plane film defects increases, or the area of film defects becomes larger. However, in the above configuration, a surface modification section is further provided to perform surface modification on the substrate surface before SAM formation. More specifically, a surface modification section is provided to impart hydroxyl groups to the substrate surface. In this way, the above configuration aims to reduce the area where SAM molecules cannot chemically adsorb, and even without the long contact time between SAM molecules and the substrate surface for forming dense SAM as shown in the previous substrate processing apparatus, the generation of film defects can be suppressed, and SAM with excellent density and protective properties can be formed efficiently in a short time.

In the above configuration, the surface modification section can also be a surface modification liquid supply section that supplies a surface modification liquid containing an alkaline solution to the surface of the substrate. The surface modification liquid supply section supplies the surface modification liquid containing the alkaline solution to the substrate surface, thereby imparting hydroxyl groups to the substrate surface. This significantly reduces the areas where SAM molecules cannot chemically adsorb, allowing more SAM molecules to chemically adsorb onto the substrate surface at a high density. As a result, SAM with excellent density and protective properties can be formed.

Furthermore, in the above-described configuration, the alkaline solution is preferably an ammonia-hydrogen peroxide mixture, ammonia water, tetramethylammonium hydroxide aqueous solution, or trimethyl-2-hydroxyethylammonium hydroxide aqueous solution.

Furthermore, in the above configuration, the surface-modified portion can also be an ultraviolet irradiation portion that irradiates ultraviolet light onto the surface of the substrate in an atmosphere containing oxygen atoms. The ultraviolet irradiation portion can impart hydroxyl groups to the surface of the substrate by irradiating the substrate surface with ultraviolet light in an atmosphere containing oxygen atoms. This significantly reduces the areas where SAM molecules cannot chemically adsorb, allowing more SAM molecules to chemically adsorb onto the substrate surface at a high density. As a result, SAM with excellent density and protective properties can be formed.

Furthermore, in the above configuration, it is preferable to further include a pretreatment liquid supply unit, which supplies a pretreatment liquid containing hydrogen fluoride to the surface of the substrate before surface modification by the surface modification unit. By supplying the pretreatment liquid containing hydrogen fluoride before surface modification of the substrate surface, the pretreatment liquid supply unit can effectively introduce hydroxyl groups during surface modification by the surface modification unit. As a result, SAM molecules can be chemically adsorbed onto the substrate surface at a further high density, thereby forming SAM with even better density and protective properties.

To address the aforementioned problems, the semiconductor manufacturing apparatus of this invention is characterized by being a semiconductor manufacturing apparatus for processing a substrate on which a laminate is disposed on its surface, wherein the laminate comprises a protected layer that serves as the object of etching and an etched layer that serves as the object of etching, which are alternately laminated. The semiconductor manufacturing apparatus further comprises: a surface modification section, which performs surface modification by applying hydroxyl groups to the surface of the protected layer; and a processing liquid supply section, which supplies a liquid to the surface-modified protected layer. The surface is supplied with a treatment liquid containing molecules capable of forming a self-tissued monolayer, thereby forming the aforementioned self-tissued monolayer; and an etching section, which uses the aforementioned self-tissued monolayer as a protective layer to selectively etch and remove the etched layer. The aforementioned molecules have functional groups capable of undergoing dehydration condensation reactions with the aforementioned hydroxyl groups. The treatment liquid supply section chemically adsorbs the aforementioned molecules onto the surface of the protected layer by means of the dehydration condensation reaction between the aforementioned hydroxyl groups and the aforementioned functional groups possessed by the aforementioned molecules.

The semiconductor manufacturing apparatus described above achieves excellent selective etching of the etchable layer by pre-forming SAM on at least the surface of the protective layer before etching the etchable layer to protect it. Furthermore, in this configuration, the surface modification section applies hydroxyl groups to the surface of the protective layer, thereby performing surface modification on that surface. Additionally, the processing liquid supply section brings a processing liquid containing SAM molecules into contact with the surface of the protective layer, thereby forming SAM. Here, SAM molecules possess functional groups capable of dehydration condensation reactions with hydroxyl groups. Therefore, if SAM molecules come into contact with the surface of the protected layer, a dehydration condensation reaction occurs between the functional groups of the SAM molecules and the hydroxyl groups on the surface of the protected layer, allowing for the chemical adsorption of SAM molecules. Furthermore, the chemically adsorbed SAM molecules undergo self-organization, thereby forming SAM. However, in the SAM formed on the surface of the protected layer, there are instances where SAM molecules cannot be chemically adsorbed onto the surface of the protected layer, resulting in film defects. Especially when the contact time between SAM molecules and the surface of the protected layer is short, the frequency of in-plane film defects increases, or the area of film defects becomes larger. However, the above configuration further includes a surface modification section, which modifies the surface of the protected layer before the formation of SAM. More specifically, it includes a surface modification section that imparts hydroxyl groups to the surface of the protected layer. In this way, the above configuration aims to reduce the areas where SAM molecules cannot chemically adsorb, and even without the prolonged contact between SAM molecules and the protected layer surface to form a dense SAM as shown in previous semiconductor manufacturing apparatuses, it can suppress the generation of film defects and efficiently form a dense SAM with excellent protective properties in a short time.

To address the aforementioned problems, the semiconductor manufacturing apparatus of the present invention is characterized in that it is a semiconductor manufacturing apparatus for processing a substrate on which a laminate is disposed on its surface. The laminate comprises alternating layers of a protected layer (which serves as the object of etching) and an etchable layer (which serves as the object of etching). The semiconductor manufacturing apparatus includes: a substrate processing unit that selectively forms an autologous monolayer on at least the surface of the protected layer; and an etching processing unit that uses the autologous monolayer as a protective layer to selectively etch and remove the etchable layer. The treatment unit comprises: a surface modification section, which performs surface modification by applying hydroxyl groups to the surface of the protected layer; and a treatment liquid supply section, which supplies the surface-modified surface of the protected layer, after surface modification by the surface modification section, with a treatment liquid containing molecules capable of forming the self-tissued monolayer, thereby forming the self-tissued monolayer. The molecules have functional groups capable of undergoing dehydration condensation reactions with the hydroxyl groups. The treatment liquid supply section chemically adsorbs the molecules onto the surface of the protected layer by means of the dehydration condensation reaction between the hydroxyl groups and the functional groups of the molecules.

The semiconductor manufacturing apparatus configured as described above includes at least: a substrate processing unit that selectively forms SAM on a protected layer; and an etching processing unit that selectively etches and removes an etchable layer. In the etching processing unit, by pre-forming SAM on at least the surface of the protected layer in the substrate processing unit before etching the etchable layer to protect it, excellent selective etching of the etchable layer can be achieved. Furthermore, in the above configuration, a surface modification unit applies hydroxyl groups to the surface of the protected layer, thereby performing surface modification on that surface. Also, a processing liquid supply unit brings a processing liquid containing SAM molecules into contact with the surface of the protected layer, thereby forming SAM. Here, SAM molecules possess functional groups capable of dehydration condensation reactions with hydroxyl groups. Therefore, if SAM molecules come into contact with the surface of the protected layer, a dehydration condensation reaction occurs between the functional groups of the SAM molecules and the hydroxyl groups on the surface of the protected layer, allowing for the chemical adsorption of SAM molecules. Furthermore, the chemically adsorbed SAM molecules undergo self-organization, thereby forming SAM. However, in the SAM formed on the surface of the protected layer, there are instances where SAM molecules cannot be chemically adsorbed onto the surface of the protected layer, resulting in film defects. Especially when the contact time between SAM molecules and the surface of the protected layer is short, the frequency of in-plane film defects increases, or the area of film defects becomes larger. However, the above configuration further includes a surface modification section that performs surface modification on the surface of the protected layer before the formation of SAM. More specifically, it includes a surface modification section that imparts hydroxyl groups to the surface of the protected layer. In this way, the above configuration aims to reduce the areas where SAM molecules cannot chemically adsorb, and even without the prolonged contact between SAM molecules and the protected layer surface to form a dense SAM as shown in previous semiconductor manufacturing apparatuses, it can suppress the generation of film defects and efficiently form a dense SAM with excellent protective properties in a short time.

In the above configuration, the surface modification section can also be a surface modification liquid supply section, which supplies a surface modification liquid containing an alkaline solution to the surface of the protected layer. By supplying the surface modification liquid containing the alkaline solution to the surface of the protected layer, hydroxyl groups can be applied to the surface of the protected layer. This significantly reduces the areas where SAM molecules cannot chemically adsorb, allowing more SAM molecules to chemically adsorb at a high density onto the surface of the protected layer. As a result, a SAM layer with excellent density and protective properties can be formed.

Furthermore, in the above-described configuration, the alkaline solution is preferably an ammonia-hydrogen peroxide mixture, ammonia water, tetramethylammonium hydroxide aqueous solution, or trimethyl-2-hydroxyethylammonium hydroxide aqueous solution.

Furthermore, in the above configuration, the surface-modified portion can also be an ultraviolet irradiation portion that irradiates the surface of the protected layer with ultraviolet light in an atmosphere containing oxygen atoms. The ultraviolet irradiation portion irradiates the surface of the protected layer with ultraviolet light in an atmosphere containing oxygen atoms, thereby imparting hydroxyl groups to the surface of the protected layer. This significantly reduces the areas where SAM molecules cannot chemically adsorb, allowing more SAM molecules to chemically adsorb at a high density onto the surface of the protected layer. As a result, a SAM with excellent density and protective properties can be formed.

Furthermore, in the above configuration, it is preferable to further include a pretreatment liquid supply unit, which supplies a pretreatment liquid containing hydrogen fluoride to the surface of the protected layer before surface modification by the surface modification unit. By supplying the pretreatment liquid containing hydrogen fluoride before surface modification of the protected layer, the pretreatment liquid supply unit facilitates the effective introduction of hydroxyl groups during surface modification by the surface modification unit. As a result, SAM molecules can be chemically adsorbed onto the surface of the protected layer at a further high density, forming SAM with even better density and protective properties. [Effects of the Invention]

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

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

[Substrate Processing Method (Manufacturing Method of Semiconductor Device)] First, the substrate processing method of this embodiment will be described below with reference to the figures. The substrate processing method of this embodiment provides, for example, a technique that enables good selective etching when forming three-dimensional structures such as three-dimensional NAND structures on the surface of a substrate.

The substrate processing method of this embodiment can be applied to a part of the process of forming a three-dimensional NAND structure on a substrate W containing silicon or the like. Therefore, the following describes an example of applying the substrate processing method of this embodiment to a semiconductor device manufacturing method, and more specifically, an example of processing a substrate W on which a multilayer body 3 with a three-dimensional structure as shown in Figures 1A and 1B is provided. Figure 1A is a schematic cross-sectional view of the multilayer body disposed on the substrate W, showing the state before the etching step. Figure 1B is a schematic cross-sectional view of the multilayer body disposed on the substrate W, showing the state after the etching step.

As shown in FIG. 2A, the laminate 3 comprises alternating layers of SiO ₂ layer 1, which functions as an interlayer insulation layer, and SiN layer 2, which functions as a sacrifice layer, deposited on the substrate W. Furthermore, a plurality of storage trenches 4 extending through the laminate 3 are provided in a direction perpendicular to the surface of the substrate W. FIG. 2A is a partially enlarged view of the portion of the laminate shown in FIG. 1A enclosed by A.

The manufacturing method of the semiconductor device according to this embodiment is shown in Figure 3. It includes at least a self-tissued monolayer (SAM) formation step S1 and an etching step S2. The SiN layer 2 is selectively etched through the storage trench 4, thereby forming a recess on the side of the storage trench 4 in the laminate 3. Figure 3 is a flowchart showing an example of the overall process of the manufacturing method of the semiconductor device according to this embodiment.

<SAM Formation Step> SAM formation step S1 is a step in which SAM, serving as a protective layer, is selectively formed on the surface of the _SiO2 layer 1, which serves as the protected layer. As shown in Figure 3, SAM formation step S1 includes at least: pretreatment step S101, surface modification step S102, treatment solution preparation step S103, film formation step S104, removal step S105, and drying step S106. Furthermore, SAM formation step S1 is equivalent to the substrate processing method of this invention.

1. Pretreatment Step Pretreatment step S101 is as follows: removing organic molecules that are physically adsorbed onto the surface of the SiO2 layer ₁ , which serves as the protective layer, and are coated on the surface of the _SiO2 layer 1 in the form of particles or thin films. This step is optional, but it is preferred to perform this step from the viewpoint of effectively performing surface modification of the substrate W in the surface modification step S102 described later. Specifically, pretreatment step S101 is performed by bringing the pretreatment liquid into contact with the surface of the substrate W.

There are no particular limitations on the method of bringing the pretreatment liquid into contact with the substrate W. Examples include: applying the pretreatment liquid to the surface of the substrate W, spraying the pretreatment liquid onto the surface of the substrate W, or immersing the substrate W in the pretreatment liquid.

One method for applying a pretreatment liquid to the surface of a substrate W is as follows: the pretreatment liquid is supplied to the center of the surface of the substrate W while the substrate W is rotated at a constant speed around its central axis. In this manner, the pretreatment liquid supplied to the surface of the substrate W flows from near the center of the substrate W towards the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered by the pretreatment liquid, forming a liquid film of the pretreatment liquid.

There are no particular limitations on the conditions for the pretreatment liquid to contact the substrate W, and there are no particular limitations on the time for the pretreatment liquid to contact the substrate W (the immersion time when the substrate W is immersed in the pretreatment liquid for pretreatment), which can be set appropriately. However, by keeping the contact time of the pretreatment liquid to less than 1 minute, excessive etching of the surface portion of the _SiO2 layer can be suppressed.

There are no particular limitations on the temperature of the pretreatment solution; it can be set appropriately as needed, such as room temperature. Furthermore, in this instruction manual, "room temperature" means a temperature range of 5°C to 35°C.

There are no particular limitations on the pretreatment solution; for example, hydrofluoric acid (e.g., HF:deionized water (DIW) = 1:100 by volume ratio) can be used.

2. Surface Modification Step ( Wet Method ) Surface modification step S102 is, for example, the following step: On the surface of the SiO2 layer ₁ as shown in Figure 4A, areas where SAM molecules are difficult to chemically adsorb are modified into areas where SAM molecules can chemically adsorb. Furthermore, the above-mentioned surface modification step S102 is a step that enables SAM molecules to be chemically adsorbed at a further high density in the areas where SAM molecules can chemically adsorb. Figure 4A is a conceptual illustration showing the surface state of the _SiO2 layer 1 before surface modification.

If surface modification is performed on the surface of _SiO2 layer 1 through surface modification step S102, as shown in Figure 4B, the surface is endowed with hydroxyl groups that can chemically adsorb SAM molecules. Figure 4B is a conceptual illustration of 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, it is performed by bringing the surface modification liquid into contact with the surface of the substrate W after pretreatment step S101. The method for bringing the surface modification liquid into contact with the surface of the substrate W is not particularly limited, and examples include: applying the surface modification liquid to the surface of the substrate W, spraying the surface modification liquid onto the surface of the substrate W, immersing the substrate W in the surface modification liquid, etc.

Furthermore, as a method for applying the surface modifier liquid to the surface of the substrate W, an example can be given as follows: the surface modifier liquid is supplied to the central portion of the surface of the substrate W while the substrate W is rotating at a constant speed around its central portion. In this way, the surface modifier liquid supplied to the surface of the substrate W flows from near the center of the substrate W's surface towards the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered by the surface modifier liquid, forming a liquid film of the surface modifier liquid.

As a surface-modifying solution, there are no particular limitations as long as it can impart hydroxyl groups to the surface of _SiO2 layer 1. Specifically, examples of surface-modifying solutions include: an ammonia-hydrogen peroxide mixture (Standard Clean-1 (SC-1)) (by volume, ammonium water ( _NH3 concentration 28%): hydrogen peroxide _{( H2O2} concentration 30%): DIW = 1:4:20), ammonia, tetramethylammonium hydroxide aqueous solution, and trimethyl-2-hydroxyethylammonium hydroxide aqueous solution, etc. Among these alkaline solutions, the ammonia-hydrogen peroxide mixture is preferred from the viewpoint of effectively imparting hydroxyl groups to the _SiO2 layer.

There are no particular limitations on the conditions for the surface modifier solution to contact the substrate W, nor is there a particular limitation on the contact time (the immersion time when the substrate W is immersed in the surface modifier solution). These conditions can be appropriately set. However, by setting the contact time of the surface modifier solution to 10 minutes or more, hydroxyl groups can be sufficiently deposited on the surface of the _SiO2 layer 1. This reduces the areas where SAM molecules (hereinafter referred to as "SAM molecules") cannot be chemically adsorbed, allowing SAM molecules to be chemically adsorbed onto the surface of the SiO2 layer ₁ at a high density. As a result, the formation of film defects can be suppressed, and SAM with excellent density and protective properties can be formed efficiently in a short time.

There are no particular limitations on the temperature of the surface modifier liquid; it can be set appropriately as needed, such as room temperature.

Furthermore, when performing the surface modification step S102 using a wet method, immediately after completing S102, a washing step to remove the surface modification solution and a drying step can be performed sequentially. The washing method in the washing step is not particularly limited; examples include supplying the washing solution to the surface of the substrate W or immersing the substrate W in the washing solution. Examples of washing solutions include toluene, decane, and 1,3-bis(trifluoromethyl)benzene. These solvents can be used alone or in combination of two or more. The washing time and temperature of the washing solution are not particularly limited and can be set appropriately as needed. The purpose of the drying step is to remove the cleaning solution remaining on the surface of the substrate W. There are no particular limitations on the drying method; for example, blowing an inert gas such as nitrogen onto the surface of the substrate W can be used. The drying time and temperature are not particularly limited and can be set appropriately as needed.

3. Treatment Solution Preparation Step S103 is the step of generating a treatment solution containing SAM molecules. The treatment solution is used to form SAM on the surface of the _SiO2 layer 1, which serves as the protected layer. The preparation of the treatment solution is carried out, for example, as follows.

First, prepare a dispersion of water to be uniformly dispersed in an organic solvent, which will serve as the main solvent. Uniform dispersion of water in an organic solvent means, for example, that water exists in the organic solvent in an emulsion state. Furthermore, the term "main solvent" refers to the solvent with the largest volume ratio when using a mixture of solvents containing multiple solvents.

Examples of organic solvents used as primary solvents include: ether solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, fluorinated solvents, and ketone solvents. There are no particular limitations on ether solvents; for example, tetrahydrofuran (THF) can be used. There are no particular limitations on aromatic hydrocarbon solvents; for example, toluene can be used. There are no particular limitations on aliphatic hydrocarbon solvents; for example, decane can be used. There are no particular limitations on fluorinated solvents; for example, 1,3-bis(trifluoromethyl)benzene can be used. There are no particular limitations on ketone solvents; for example, methyl ethyl ketone can be used. These solvents can be used alone or in mixtures of two or more. Among the solvents listed, aromatic hydrocarbon solvents are preferred from the viewpoint of affinity for water, and toluene is particularly preferred. Furthermore, regarding the organic solvent as the main solvent, it is preferable to have low solubility in water. This allows water to be well dispersed in the organic solvent. Examples of organic solvents with low solubility in water include, for example, toluene, as mentioned above.

The amount of water added to the dispersion is preferably in the range of 50 ppm to 200 ppm, and more preferably in the range of 50 ppm to 150 ppm. By setting the amount of water added to 50 ppm or more, the hydrolysis reaction of the functional groups exhibiting hydrolytic reactivity in the SAM molecules added during the preparation of the treatment solution can be prevented from becoming insufficient. That is, during the formation stage of the treatment solution, a sufficient amount of SAM molecules with introduced hydroxyl groups can be present in the treatment solution. As a result, even if the treatment solution is in contact with the substrate surface for a long time to form dense SAM, as shown in the previous substrate treatment method, the generation of film defects can be suppressed and SAM with excellent density can be formed. On the other hand, by setting the amount of water added to below 200 ppm, excessive aggregation of SAM molecules with hydroxyl groups due to dehydration condensation reaction can be suppressed. As a result, the density reduction of SAM molecules chemically adsorbed on the substrate surface can be suppressed, thus forming SAM with excellent density.

There are no particular limitations on the method for preparing the dispersion. For example, methods include mixing an organic solvent with water while applying ultrasound, and applying ultrasound after mixing an organic solvent with water. By applying ultrasound, phase separation into an organic solvent phase and an aqueous phase can be prevented. Specifically, the ultrasound application conditions, such as application time, frequency, and sound intensity, are not particularly limited as long as they contribute to the dispersion of water in the organic solvent and can be set appropriately as needed. Furthermore, there are no particular limitations on the method of applying ultrasound. For example, methods include immersing an ultrasonic transducer in the mixture and applying ultrasound by vibrating the transducer.

Furthermore, the preparation of the dispersion is preferably carried out in an inert gas atmosphere such as nitrogen. When the preparation is carried out in an environment where moisture is present, the moisture in the atmosphere dissolves in the mixture (or dispersion), resulting in a dispersion with the specified water content that cannot be obtained, which is undesirable.

Next, a material capable of forming SAM (hereinafter referred to as "SAM forming material") is added to the prepared dispersion to prepare a treatment solution. It is preferable to perform the addition of the SAM forming material to the dispersion, and after its addition, without applying ultrasound. By not applying ultrasound, the treatment solution can be generated in a manner where SAM molecules do not aggregate. By generating the treatment solution in a manner where SAM molecules do not aggregate, SAM can be well formed in the film formation step S104 described later.

As a SAM-forming material, there are no particular limitations as long as it contains a functional group exhibiting hydrolytic reactivity and is capable of forming SAM molecules. Furthermore, it is preferable to use a material with high affinity (solubility) for the aforementioned organic solvents. Specifically, SAM-forming materials include, for example, organosilicon compounds such as _{octadecyltrichlorosilane} ( _{C18H37SiCl3 )} , _{decyltrichlorosilane (C10H21SiCl3 ) , trichloropropylsilane} ( _C3H7SiCl3 ), and _{trichloromethylsilane} ( _{CH3SiCl3 )} . These organosilicon compounds have trichlorosilyl groups as functional groups exhibiting hydrolytic reactivity.

SAM molecules added to the treatment solution before hydrolysis exhibit functional groups that are reactive to hydrolysis. Therefore, when a SAM forming material is added to a dispersion, these functional groups undergo hydrolysis with water molecules that are uniformly dispersed and present in the dispersion. In this way, the reactive functional group becomes a hydroxyl group (a functional group capable of undergoing dehydration condensation with a hydroxyl group). For example _, when the SAM molecule is octadecyltrichlorosilane, the following reaction occurs: _{C18H37SiCl3 + 3H2O} → _C18H37Si (OH) ₃ + _{3HCl. As} a result, a treatment solution is obtained in which SAM molecules containing hydroxyl (or silanol) groups do not aggregate. Therefore, by pre-preparing a treatment solution containing SAM molecules with hydroxyl groups, the rate-limiting hydrolysis reaction in the SAM film formation process can be omitted. As a result, SAM can be formed in a shorter time compared to the previous treatment solution.

The amount of SAM forming material added relative to the total mass of the treatment fluid is preferably in the range of 0.05% by mass or more and 5% by mass or less.

The treatment solution may also contain known additives, to the extent that they do not impair the effectiveness of the invention. There are no particular limitations on the additives; for example, stabilizers and surfactants may be included.

The preparation of the treatment solution is preferably carried out under static conditions. More specifically, it is not ideal to apply mechanical forces such as stirring and shaking to the dispersion when adding the SAM forming material. When applying mechanical forces such as stirring and shaking to the dispersion while adding the SAM forming material, SAM molecules may aggregate. However, by adding SAM forming material to the static dispersion to adjust the treatment solution, the aggregation of SAM molecules can be further suppressed to form a treatment solution.

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

The treatment fluid preparation step S103 can be performed, for example, at room temperature and pressure. Furthermore, in this manual, "room temperature" refers to pressure near the standard atmospheric conditions (standard atmospheric pressure), which means a temperature of approximately 25°C and an atmospheric pressure of approximately 101 kPa. Also, "room temperature" includes conditions that are slightly positive or negative relative to standard atmospheric pressure.

4. Film Formation Step S104 is a step in which a treatment solution containing SAM forming material is brought into contact with the surface of the substrate W to form SAM.

There are no particular limitations on the method of bringing the treatment liquid into contact with the substrate W. Examples include: applying the treatment liquid to the surface of the substrate W, spraying the treatment liquid onto the surface of the substrate W, immersing the substrate W in the treatment liquid, etc.

One method for applying a treatment liquid to the surface of a substrate W is as follows: the treatment liquid is supplied to the center of the surface of the substrate W while the substrate W is rotated at a constant speed around its central axis. In this manner, the treatment liquid supplied to the surface of the substrate W flows from near the center of the substrate W's surface towards the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered by the treatment liquid, forming a liquid film of the treatment liquid.

There are no particular limitations on the conditions under which the treatment liquid contacts the substrate W. However, compared to the case of forming SAM using the previous method, the film formation step S104 of this embodiment can shorten the contact time of the treatment liquid. Specifically, the time required for the SAM formation step S1 (when the substrate W is immersed in the treatment liquid) can be appropriately set within the range of 1 minute to 1540 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 formation process of SAM will be explained in more detail, taking the case where the SAM forming material is octadecyltrichlorosilane as an example.

If a treatment solution is supplied to the surface of substrate W as shown in Figure 4C, then SAM molecules 5 with hydroxyl groups incorporated into octadecyltrichlorosilane are dispersed in the treatment solution at the time of supply. Figure 4C is an explanatory diagram showing the situation where the treatment solution is supplied to the surface of _SiO2 layer 1.

Here, hydroxyl groups are introduced onto the surface of SiO2 layer ₁ via the aforementioned surface modification step S102. Therefore, as shown in Figure 5A, SAM molecules 5 undergo a dehydration condensation reaction with the hydroxyl groups. More specifically, the hydroxyl groups of SAM molecules 5 undergo a dehydration condensation reaction with the hydroxyl groups on the surface of _SiO2 layer 1, thereby forming siloxane bonds, whereby SAM molecules 5 are chemically adsorbed onto the surface of _SiO2 layer 1. SAM molecules 5 exist in the treatment solution in a state where mutual aggregation is suppressed. Therefore, the dehydration condensation reaction between the hydroxyl groups of SAM molecules 5 and the hydroxyl groups on the surface of _SiO2 layer 1, which becomes the rate-limiting stage in the SAM film formation process, can be promoted. Furthermore, SAM molecules 5 can be chemically adsorbed onto the surface of _SiO2 layer 1 at a high density. Moreover, Figure 5A is an explanatory diagram showing the chemical adsorption of SAM molecules 5 onto the surface of SiO2 layer ₁ .

Subsequently, if SAM molecules 5 are chemically adsorbed at high density on the surface of _SiO2 layer 1, island-like structures of SAM molecules 5 appear on the surface. Then, within each island, SAM molecules 5 self-organize and grow (expand) through hydrophobic or electrostatic interactions, ultimately forming SAM6 (see Figure 5B). Figure 5B is an illustration of the self-organization of SAM molecules 5 on the surface of _SiO2 layer 1 to form SAM6.

5. Removal Step S105 is a step to remove the treatment solution remaining on the surface of _SiO2 layer 1 after film formation step S104. This removes excess SAM molecules 5 that do not contribute to the formation of SAM6, and more specifically, removes SAM molecules 5 that are not chemically adsorbed on the surface of _SiO2 layer 1. As a result, it prevents the formation of a film containing unadsorbed SAM molecules 5 on SAM6, thus forming a good monolayer.

There are no particular limitations on the method for removing the treatment liquid from the surface of the _SiO2 layer 1. For example, methods such as applying the removal liquid to the surface of the substrate W, spraying the removal liquid onto the surface of the substrate W, or immersing the substrate W in the removal liquid are all possible.

One method for applying a removal liquid to the surface of a substrate W is as follows: the removal liquid is supplied to the center of the surface of the substrate W while the substrate W is rotated at a constant speed around its central axis. In this manner, the removal liquid supplied to the surface of the substrate W flows from near the center of the surface of the substrate W towards the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire surface of the substrate W. As a result, the treatment liquid or the like on the surface of the substrate W is replaced by the removal liquid, and the entire surface of the substrate W is covered by the removal liquid, forming a liquid film of the removal liquid.

When the SAM forming material is octadecyltrichlorosilane, the surface of the SiO2 layer ₁ in removal step S105 is shown in Figure 5C. As shown in Figure 5C, the SAM molecules 5 that do not contribute to the formation of SAM6 are removed from the surface of the _SiO2 layer ₁ on the substrate W by the removal liquid. Figure 5C is an explanatory diagram showing the removal of excess SAM molecules 5 from the surface of the SiO2 layer 1 in removal step S105.

There are no particular limitations on the removal solution, but it is preferably an organic solvent that dissolves the SAM forming material and has low solubility in water. If the removal solution can dissolve the SAM forming material, it can effectively remove excess SAM molecules that do not contribute to SAM formation from the surface. More specifically, examples of removal solutions include toluene, decane, and 1,3-bis(trifluoromethyl)benzene. These solvents can be used alone or in mixtures of two or more.

6. Drying Step The purpose of drying step S106 is to remove the removal liquid remaining on the surface of the substrate W. There are no particular limitations on the drying method; for example, blowing an inert gas such as nitrogen onto the surface of the substrate W is acceptable. The drying time and temperature are not particularly limited as long as the removal liquid is removed to a certain extent, and can be set appropriately as needed.

Based on the above, in the SAM formation step S1, as shown in Figure 5C, SAM6 with excellent density and protective properties can be formed on the surface of SiO2 layer _1. In this embodiment, hydroxyl groups are introduced into the surface of SiO2 layer ₁ by performing a surface modification step S102. This allows SAM molecules 5 to be chemically adsorbed in areas where they cannot be chemically adsorbed. Furthermore, in areas where SAM molecules 5 can be chemically adsorbed, hydroxyl groups can be further introduced to allow SAM molecules 5 to be chemically adsorbed onto the surface of _SiO2 layer 1 at a high density. As a result, even without allowing SAM molecules 5 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 SAM6 with excellent density and protective performance can be formed efficiently in a short time.

Furthermore, in this embodiment, immediately after completing the drying step S106, a rinsing step and other drying steps can be performed. The rinsing step removes the cleaning solution from the surface of the _SiO2 layer 1. Additionally, the other drying steps remove the rinsing solution used in the rinsing step.

There are no particular limitations on the rinsing solution used in the rinsing step; for example, DIW can be used. There are also no particular limitations on the method of supplying the rinsing solution to the surface of the substrate W; for example, methods such as applying the rinsing solution to the surface of the substrate W, spraying the rinsing solution onto the surface of the substrate W, or immersing the substrate W in the rinsing solution can be used.

One method for applying a rinsing solution to the surface of a substrate W is as follows: The rinsing solution is supplied to the center of the surface of the substrate W while the substrate W is rotated at a constant speed around its central axis. In this manner, the rinsing solution supplied to the surface of the substrate W flows from near the center of the surface of the substrate W towards the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire surface of the substrate W. As a result, the removal liquid on the surface of the substrate W is replaced by the rinsing solution, and the entire surface of the substrate W is covered by the rinsing solution, forming a liquid film of the rinsing solution.

The purpose of other drying steps is to remove the rinsing solution remaining on the surface of the substrate W. There are no particular limitations on the drying method; for example, blowing an inert gas such as nitrogen onto the surface of the substrate W is acceptable. Drying conditions such as drying time and temperature are not particularly limited as long as they are sufficient to remove the rinsing solution and can be set appropriately as needed.

<Etching Step (Monolithic)> Etching step S2 is a step in which the SiN layer 2, which serves as the sacrifice layer and is the layer to be etched, is selectively etched. More specifically, it is a step in which the etching solution is brought into contact with the SiN layer 2 through the storage trench 4 to remove the SiN layer 2. In this step, SAM6 acts as a protective layer to protect the SiO ₂ layer 1. In this way, the etching of the SiO ₂ layer 1 can be effectively suppressed.

One method for applying etching solution to the surface of substrate W is as follows: In the case of monolithic operation, the etching solution is supplied to the center of the surface of substrate W while the substrate W is rotated at a constant speed around its central axis. In this way, the etching solution supplied to the surface of substrate W flows from near the center of the substrate W's surface to the periphery of the substrate W due to the centrifugal force generated by the rotation of substrate W, and diffuses to the entire surface of substrate W. As a result, the entire surface of substrate W is covered by etching solution, forming a liquid film of the etching solution.

The etching solution can be appropriately set considering factors such as the constituent material of the layer to be etched or the corrosion rate. In the case where the layer to be etched is SiN layer 2, as shown in this embodiment, an aqueous solution of phosphoric acid ( _H₃PO₄ ) or hydrofluoric acid (e.g., HF:DIW = 1:100 by volume ratio) can be used as the etching solution. Furthermore, the concentration of the etching solution can also be appropriately set considering _factors such as the constituent material of the layer to be etched or the corrosion rate.

Furthermore, the etching temperature (i.e., the temperature of the etching solution) and the corrosion rate of the etched layer can be appropriately set by taking into account the constituent materials of the etched layer.

Furthermore, immediately after completing etching step S2, it is preferable to sequentially perform a rinsing step to remove the etching solution and a drying step. The rinsing method is not particularly limited; examples include supplying the 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; examples include DIW. Furthermore, the rinsing time and the temperature of the rinsing solution are not particularly limited and can be set appropriately as needed. The purpose of the drying step is to remove any remaining rinsing solution from the surface of the substrate W. There are no particular limitations on the drying method; for example, blowing an inert gas such as nitrogen onto the surface of the substrate W can be used. There are no particular limitations on the drying time and drying temperature, and they can be set appropriately 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 the _SiO2 layer 1, since SAM6, with its excellent density and protective properties, coats its surface for protection, it can prevent the _SiO2 layer 1 from being etched, or prevent etched silicon precipitates from being released and adhering to the surface of the SiO2 layer _1. This also increases the allowable range of silicon concentration in the etching solution such as phosphoric acid. Moreover, Figure 2C is a partially enlarged view of the portion surrounded by B in the laminate of Figure 1B, showing the state of the SiN layer 2 under etching.

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

The semiconductor manufacturing apparatus 100 of this embodiment is a monolithic processing unit used to form SAM and etch the etched layer. As shown in FIG6, it includes: a substrate holding section 110, which holds the substrate W; a pretreatment liquid supply section 120, which supplies pretreatment liquid to the surface Wf of the substrate W; a surface modification liquid supply section (surface modification section) 130, which supplies surface modification liquid to the surface Wf of the substrate W; and a processing liquid supply section 140, which... The apparatus includes: a treatment fluid supplying a processing fluid to the surface Wf of the substrate W; an ultrasonic application unit; a removal fluid supply unit 150 supplying removal fluid; an inert gas supply unit (not shown) supplying inert gas; an etching fluid supply unit (etching unit) 160; a chamber 170, which is a container for housing the substrate W; an anti-spray shield 180, which traps the treatment fluid; a rotary drive unit 190, which drives the arms of each part to rotate independently; and a control unit 300. Furthermore, the semiconductor manufacturing apparatus 100 may also include a loading/unloading mechanism (not shown) for moving the substrate W in or out. Furthermore, Figure 6 is an explanatory diagram showing the schematic structure of the semiconductor manufacturing apparatus 100 according to this embodiment. In Figure 7, the XYZ orthogonal coordinate axes are appropriately represented to clarify the directional relationship of the figures. Here, the XY plane represents the horizontal plane, and the +Z direction represents vertical upwards.

<Substrate Holding Section> The substrate holding section 110 is a mechanism for holding the substrate W. As shown in FIG. 7, it holds the substrate W in a generally horizontal position with its surface Wf facing upwards and allows it to rotate. The substrate holding section 110 has a rotating chuck 113 integrally formed by a rotating base 111 and a rotating spindle 112. The rotating base 111 is generally circular in plan view, and a hollow rotating spindle 112 extending in a generally vertical direction is fixed to its center. The rotating spindle 112 is connected to the rotation axis of a suction cup rotating mechanism 114 containing a motor. The suction cup rotating mechanism 114 is housed within a cylindrical sleeve 115, and the rotating spindle 112 is freely supported for rotation around the vertical rotation axis J1 by the sleeve 115.

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

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

<Pretreatment Liquid Supply Unit> The pretreatment liquid supply unit 120 of this embodiment is a mechanism for supplying pretreatment liquid to the surface Wf of the substrate W. As shown in FIG. 6, the pretreatment liquid supply unit 120 includes a pretreatment liquid storage unit 121, a nozzle 122, and a support arm 123.

As shown in FIG7, the pretreatment liquid storage unit 121 includes a pressurization unit 124 and a pretreatment liquid tank 125. Furthermore, FIG7 is an explanatory diagram showing the schematic structure of the pretreatment liquid storage unit 121 in the pretreatment liquid supply unit 120.

The pressurization unit 124 includes: a nitrogen supply source 124a that serves as a supply source for pressurizing the gas in the pretreatment liquid tank 125, a pump (not shown) for pressurizing the nitrogen, a nitrogen supply pipe 124b, and a valve 124c installed along the path of the nitrogen supply pipe 124b.

Nitrogen supply pipe 124b is connected to the pretreatment liquid tank 125. Valve 124c is electrically connected to the control unit 300, and its opening and closing can be controlled by the operation commands of the control unit 300. If valve 124c is opened by the operation command of the control unit 300, nitrogen can be supplied to the pretreatment liquid tank 125.

The pretreatment liquid tank 125 also includes a stirring unit for stirring the pretreatment liquid within the tank and a temperature adjustment unit for adjusting the temperature of the pretreatment liquid (neither shown). The stirring unit can be, for example, equipped with a rotating part for stirring the pretreatment liquid and a stirring control unit for controlling the rotation of the rotating part. The stirring control unit is electrically connected to the control unit 300, and the rotating part, for example, has a spiral-shaped stirring blade at the lower end of the rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby causing the rotating part to rotate, which allows the stirring blade to stir the pretreatment liquid. As a result, the concentration and temperature of the pretreatment liquid within the pretreatment liquid tank 125 become uniform.

Furthermore, a discharge pipe 125a for supplying pretreatment liquid to the nozzle 122 is connected to the pretreatment liquid tank 125. A discharge valve 125b is provided along the path of the discharge pipe 125a. The discharge valve 125b is electrically connected to the control unit 300. Thus, the opening and closing of the valve can be controlled by the operation command of the control unit 300. If the discharge valve 125b is opened by the operation command of the control unit 300, the pretreatment liquid is pressurized to the nozzle 122 through the discharge pipe 125a.

The nozzle 122 is mounted on the front end of the horizontally extending support arm 123 and is positioned above the rotating base 111 when the pretreatment fluid is sprayed. The support arm 123 is connected to the rotary drive unit 190 via a rotating shaft (not shown). The rotary drive unit 190 is electrically connected to the control unit 300 and rotates the support arm 123 by means of an operation command from the control unit 300. As the support arm 123 rotates, the nozzle 122 also moves.

<Surface Modifier Liquid Supply Unit (Surface Modifier Unit)> The surface modifier liquid supply unit 130 of this embodiment is a mechanism for supplying surface modifier liquid to the surface Wf of the substrate W. As shown in FIG. 6, the surface modifier liquid supply unit 130 includes a surface modifier liquid storage unit 131, a nozzle 132, and a support arm 133.

As shown in FIG8, the surface modifier liquid storage unit 131 has the function of supplying surface modifier liquid to the nozzle 132, and includes a pressurization unit 134 and a surface modifier liquid tank 135. FIG8 is an explanatory diagram showing the schematic structure of the surface modifier liquid storage unit 131 in the surface modifier liquid supply unit 130.

The pressurization unit 134 includes: a nitrogen supply source 134a that serves 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 installed in the middle of the path of the nitrogen supply pipe 134b.

Nitrogen supply pipe 134b is connected to the surface modification liquid tank 135. Valve 134c is electrically connected to the control unit 300, and its opening and closing can be controlled by the operation commands of the control unit 300. If valve 134c is opened by the operation command of the control unit 300, nitrogen can be supplied to the 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 tank 135, and a temperature adjusting unit for adjusting the temperature of the surface modification liquid (neither shown). As the stirring unit, examples include a rotating unit for stirring the surface modification liquid within the 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, and the rotating unit, for example, has a helical stirring blade at the lower end of its rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby causing the rotating unit to rotate, whereby the stirring blade can be used to stir the surface modification liquid. As a result, the concentration and temperature of the surface modifier can be made uniform within the surface modifier bath 135.

Furthermore, a discharge pipe 135a for supplying the surface-modifying liquid to the nozzle 132 is connected to the surface-modifying liquid tank 135. A discharge valve 135b is provided along the path of the discharge pipe 135a. The discharge valve 135b is electrically connected to the control unit 300. Thus, the opening and closing of the discharge valve 135b can be controlled by the operation command of the control unit 300. If the discharge valve 135b is opened by the operation command of the control unit 300, the surface-modifying liquid is pressurized to the nozzle 132 through the discharge pipe 135a.

The nozzle 132 is mounted on the front end of the horizontally extending support arm 133 and is positioned above the rotating base 111 when spraying the surface modifier liquid. The support arm 133 is connected to the rotary drive unit 190 via a rotary shaft (not shown). The rotary drive unit 190 is electrically connected to the control unit 300 and rotates the support arm 133 by means of an operation command from the control unit 300. The nozzle 132 also moves along with the rotation of the support arm 133.

<Processing Fluid Supply Unit> The processing fluid supply unit 140 of this embodiment is a mechanism for supplying processing fluid to the surface Wf of the substrate W. As shown in FIG. 6, the processing fluid supply unit 140 includes a processing fluid storage unit 141, a nozzle 142, and a support arm 143.

As shown in FIG. 9, the processing fluid storage unit 141 includes: an organic solvent supply unit 144, a water supply unit 145, a SAM forming material supply unit 146, a processing fluid tank 147, a temperature adjustment unit 148, and an inert gas supply unit 149. Furthermore, FIG. 9 is an explanatory diagram showing the schematic configuration of the processing fluid storage unit 141 and the ultrasonic application unit 191 in the processing fluid supply unit 140.

The organic solvent supply unit 144 includes: an organic solvent storage unit 144a for storing organic solvent, an organic solvent supply pipe 144b for supplying organic solvent to the treatment liquid tank 147, and a valve 144c disposed midway along the path of the organic solvent supply pipe 144b. Furthermore, the valve 144c is electrically connected to the control unit 300. Therefore, the opening and closing of the valve 144c can be controlled by an operation command from the control unit 300. If the valve 144c is opened by an operation command from the control unit 300, the organic solvent is supplied to the treatment liquid tank 147 via the organic solvent supply pipe 144b. Furthermore, the organic solvent in the organic solvent storage section 144a is pressurized and delivered to the organic solvent supply pipe 144b by a pressurization means not shown. Also, there are no particular limitations on the pressurization means, and known means such as pumps can be used.

The water supply unit 145 includes: a water storage unit 145a for storing water; a water supply pipe 145b for supplying water to the treatment liquid tank 147; and a valve 145c installed along the path of the water supply pipe 145b. The valve 145c is electrically connected to the control unit 300. Therefore, the opening and closing of the valve 145c can be controlled by the operation command of the control unit 300. If the valve 145c is opened by the operation command of the control unit 300, water is supplied to the treatment liquid tank 147 through the water supply pipe 145b. Furthermore, the water in the water storage unit 145a is pressurized by a pressurization means (not shown) and sent to the water supply pipe 145b. Furthermore, as a pressurization method, there are no particular limitations, and known methods such as using pumps can be used.

The SAM forming material supply unit 146 includes: a SAM forming material storage unit 146a for storing SAM forming material; a SAM forming material supply pipe 146b for supplying SAM forming material to the processing liquid tank 147; and a valve 146c disposed midway along the path of the SAM forming material supply pipe 146b. Furthermore, the valve 146c is electrically connected to the control unit 300. Therefore, the opening and closing of the valve 146c can be controlled by the operation command of the control unit 300. If the valve 146c is opened by the operation command of the control unit 300, the SAM forming material is supplied to the processing liquid tank 147 via the SAM forming material supply pipe 146b. Furthermore, the SAM forming material in the SAM forming material storage section 146a is pressurized and fed to the SAM forming material supply pipe 146b by a pressurization means not shown. Also, there are no particular limitations on the pressurization means, and known means such as pumps can be used.

The treatment liquid tank 147 mixes the organic solvent supplied by the organic solvent supply unit 144 with the water supplied by the water supply unit 145. Ultrasonic waves are applied to the resulting mixture by the ultrasonic application unit 191, thereby generating a dispersion in which water is uniformly dispersed in the organic solvent. Alternatively, this dispersion can also be generated by simultaneously mixing the organic solvent supplied by the organic solvent supply unit 144 with the water supplied by the water supply unit 145 and applying ultrasonic waves by the ultrasonic application unit 191. Furthermore, by storing the generated dispersion, SAM forming material is supplied from the SAM forming material supply unit 146 to generate the treatment liquid.

The processing liquid tank 147 may also include a temperature adjustment unit 148 for adjusting the temperature of the dispersion or processing liquid stored inside. The temperature adjustment unit 148 is electrically connected to the control unit 300. The control unit 300 issues an operation command to the temperature adjustment unit 148, thereby controlling the liquid temperature of the dispersion during dispersion generation. This prevents the water in the dispersion from vaporizing (evaporating), thus avoiding changes in the composition of the dispersion.

The inert gas supply unit 149 includes: an inert gas supply source 149a for supplying inert gas to the treatment liquid tank 147; a pump (not shown) for pressurizing the inert gas; an inert gas supply pipe 149b; and a valve 149c provided in the middle of the path of the inert gas supply pipe 149b.

Inert gas supply pipe 149b is connected to the treatment liquid tank 147. Valve 149c is electrically connected to control unit 300, and its opening and closing can be controlled by operation commands from control unit 300. If the valve is opened by operation commands from control unit 300, inert gas can be supplied to treatment liquid tank 147. This allows for the generation of dispersion and treatment liquid in an inert gas atmosphere. Furthermore, there is no particular limitation on the inert gas used; for example, nitrogen can be used.

Furthermore, a discharge pipe 147a for supplying the treatment fluid to the nozzle 142 is connected to the treatment fluid tank 147. A discharge valve 147b is provided along the path of the discharge pipe 147a. The discharge valve 147b is electrically connected to the control unit 300. Thus, the opening and closing of the discharge valve 147b can be controlled by the operation command of the control unit 300. If the discharge valve 147b and valve 149c are opened by the operation command of the control unit 300, and valves 144c, 145c and 146c are closed at the same time, the treatment fluid is pressurized to the nozzle 142 through the discharge pipe 147a.

The nozzle 142 is mounted on the front end of the horizontally extending support arm 143 and is positioned above the rotating base 111 when spraying the treatment fluid. The support arm 143 is connected to the rotary drive unit 190 via a rotary shaft (not shown). The rotary drive unit 190 is electrically connected to the control unit 300 and rotates the support arm 143 by means of an operation command from the control unit 300. As the support arm 143 rotates, the nozzle 142 also moves.

<Ultrasonic Application Unit> As shown in Figure 9, the ultrasonic application unit 191 is a mechanism that applies ultrasonic waves during the generation of a dispersion in the treatment liquid tank 147 of the treatment liquid supply unit 140. The ultrasonic application unit 191 is electrically connected to the control unit 300, and the application of ultrasonic waves can be controlled by operation commands from the control unit 300.

The ultrasonic application unit 191 includes, for example, at least: an ultrasonic transducer disposed within the treatment liquid tank 147; and an oscillator (neither shown) that applies a driving voltage to the ultrasonic transducer. The ultrasonic transducer may be an example comprising a piezoelectric element such as a piezoelectric ceramic, and a pair of electrodes disposed on the piezoelectric element. The pair of electrodes is in contact with the piezoelectric element 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 transducer according to the operation command of the control unit 300, and applies the driving voltage between the pair of electrodes, thereby applying a driving voltage to the piezoelectric element. The piezoelectric element, which is driven by an applied voltage, repeatedly contracts and expands according to the driving voltage from the oscillator, thereby generating vibration. In this way, ultrasound can be applied to the mixture of water and organic solvent stored in the treatment liquid tank 147.

<Removing Liquid Supply Unit> The removing liquid supply unit 150 of this embodiment is a mechanism for supplying removing liquid to the surface Wf of the substrate W. As shown in FIG. 6, the removing liquid supply unit 150 includes a removing liquid storage unit 151, a nozzle 152, and a support arm 153.

As shown in FIG10, the cleaning fluid storage unit 151 has the function of supplying cleaning fluid to the nozzle 152, and includes a pressurization unit 154 and a cleaning fluid tank 155. FIG10 is an explanatory diagram showing the schematic structure of the cleaning fluid storage unit 151 in the cleaning fluid supply unit 150.

The pressurization unit 154 includes: a nitrogen supply source 154a that serves as a supply source for pressurizing the gas in the removal liquid tank 155; a pump (not shown) for pressurizing the nitrogen; a nitrogen supply pipe 154b; and a valve 154c installed along the path of the nitrogen supply pipe 154b.

Nitrogen supply pipe 154b is connected to the removal liquid tank 155. Valve 154c is electrically connected to the control unit 300, and its opening and closing can be controlled by operation commands from the control unit 300. If valve 154c is opened by operation commands from the control unit 300, nitrogen can be supplied to the removal liquid tank 155.

The removal liquid tank 155 may also include a stirring unit for agitating the removal liquid within the tank 155 and a temperature adjustment unit for adjusting the temperature of the removal liquid (neither shown). As the stirring unit, examples include a rotating unit for agitating the removal liquid within the tank 155 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, and the rotating unit, for example, has a spiral-shaped stirring blade at the lower end of its rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby causing the rotating unit to rotate, which in turn allows the stirring blade to agitate the removal liquid. As a result, the concentration and temperature of the removal liquid within the removal liquid tank 155 become uniform.

Furthermore, a discharge pipe 155a is connected to the removal fluid tank 155 to supply the removal fluid to the nozzle 152. A discharge valve 155b is provided along the path of the discharge pipe 155a. The discharge valve 155b is electrically connected to the control unit 300. Therefore, the opening and closing of the discharge valve 155b can be controlled by the operation command of the control unit 300. If the discharge valve 155b is opened by the operation command of the control unit 300, the removal fluid is pressurized to the nozzle 152 through the discharge pipe 155a.

The nozzle 152 is mounted on the front end of the horizontally extending support arm 153 and is positioned above the rotating base 111 when spraying the cleaning fluid. The support arm 153 is connected to the rotary drive unit 190 via a rotary shaft (not shown). The rotary drive unit 190 is electrically connected to the control unit 300 and rotates the support arm 153 by means of an operation command from the control unit 300. As the support arm 153 rotates, the nozzle 152 also moves.

<Inert Gas Supply Unit> The inert gas supply unit is a mechanism for supplying inert gas to the surface Wf of the substrate W. This inert gas supply unit includes: an inert gas storage section, a nozzle, and a support arm (none shown).

The inert gas storage unit has the function of supplying inert gas to the nozzle, and includes: an inert gas tank for storing inert gas; an inert gas temperature adjustment unit for adjusting the temperature of the inert gas stored in the inert gas tank; and piping. Examples of inert gases stored in the inert gas tank include, for example, nitrogen.

The inert gas temperature adjustment unit is electrically connected to the control unit 300. The temperature of the inert gas stored in the inert gas tank is adjusted by heating or cooling the inert gas through the operation commands of the control unit 300. There are no particular limitations on the inert gas temperature adjustment unit. For example, a Peltier element or a temperature-adjustable water pipe can be used.

The inert gas storage unit is connected to the nozzle pipeline via piping, and valves are installed along the piping path. The inert gas in the inert gas tank is pressurized and sent to the piping by a pressurization means (not shown). Furthermore, pressurization can be achieved not only by using a pump or the like, but also by compressing and storing the inert gas in the inert gas tank.

The valve is electrically connected to the control unit 300 and is normally in the closed state. The opening and closing of the valve is controlled by the operation command of the control unit 300. If the valve is opened by the operation command of the control unit 300, inert gas is supplied to the surface Wf of the substrate W through the nozzle via the piping.

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

<Etching Solution Supply Unit (Etching Unit)> The etching solution supply unit 160 is a mechanism for supplying etching solution to the surface Wf of the substrate W. As shown in FIG. 6, the etching solution supply unit 160 includes an etching solution storage unit 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. Furthermore, 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 solution tank 164 may also be equipped with a stirring unit (not shown) for stirring the etching solution within the tank. Examples of such a stirring unit include a rotating part for stirring the etching solution and a stirring control unit for controlling the rotation of the rotating part. The stirring control unit is electrically connected to the control unit 300. The rotating part, for example, has a spiral-shaped stirring blade at the lower end of its rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby causing the rotating part to rotate, which in turn stirs the etching solution using the stirring blade. As a result, the concentration and temperature of the etching solution within the etching solution tank 164 can be made uniform.

A mixer 168 is provided in the etching solution tank 164, which is capable of mixing the reagents and DIW from an external supply source (not shown) and preparing the etching solution to a specified concentration. The reagents are solutes that function as etching agents. Examples of reagents include phosphoric acid or hydrogen fluoride, as mentioned above.

Furthermore, a discharge pipe 169 for supplying the etching solution to the nozzle 162 is connected to the etching solution tank 164 via piping. A temperature regulator 165, a liquid delivery pump 166, and a particle filter 167 are sequentially installed from upstream to downstream along the path of the discharge pipe 169. 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 solution supplied to the nozzle 162 to be controlled by the operation commands of the control unit 300. Furthermore, if the liquid delivery pump 166 is controlled by the operation commands of the control unit 300, the etching solution can be pressurized and delivered to the nozzle 162 via the discharge pipe 169. The particle filter 167 can remove particles and other foreign matter from the etching solution.

The nozzle 162 is mounted on the front end of the horizontally extending support arm 163 and is positioned above the rotating base 111 when the etching solution is sprayed. The support arm 163 is connected to the rotary drive unit 190 via a rotary shaft (not shown). The rotary drive unit 190 is electrically connected to the control unit 300 and rotates the support arm 163 by means of an operation command from the control unit 300. As the support arm 163 rotates, the nozzle 162 also moves.

<Anti-splash shield> The anti-splash shield 180 is configured to surround the rotating base 111. The anti-splash shield 180 is connected to a lifting drive mechanism (not shown) and can be raised and lowered vertically. When processing fluid or the like is supplied to the surface Wf of the substrate W, the anti-splash shield 180 is positioned at a predetermined position by the lifting drive mechanism and surrounds the substrate W, which is held by the suction cup pin 116, from the side. This captures any processing fluid or the like that that spills from the substrate W or the rotating base 111.

<Control Unit> The control unit 300 is electrically connected to each part of the semiconductor manufacturing apparatus to control the operation of each part. The control unit 300 is composed of a computer having an operation unit and a storage unit. The operation unit uses a CPU to perform various calculations. The storage unit includes: a ROM as dedicated memory for storing board processing programs and etching processing programs; RAM as memory that stores various information and can be freely read and written; and a magnetic disk pre-stored with control software or data. The disk pre-stores the generation (mixing) conditions for the dispersion and processing fluids; the supply conditions for the pretreatment fluid, surface modifier, processing fluid, removal fluid, inert gas, and etching solution; the ultrasonic application conditions; the rinsing conditions; the drying conditions; the SAM film formation conditions; and the processing conditions, including etching conditions. The CPU reads the processing conditions into RAM and controls the various parts of the semiconductor manufacturing apparatus according to their contents.

(Second Embodiment) The second embodiment of the present invention will be described below. This embodiment differs from the first embodiment in that it employs a dry method based on ultraviolet irradiation for the surface modification step. It also differs in that it uses a batch etching step instead of a single-wafer method. With this configuration, compared to previous film deposition methods, it is possible to efficiently form SAM with high film density and excellent compactness on the substrate surface in a short time, effectively suppressing or reducing film defects and providing excellent protection.

[Substrate Processing Method (Method for Manufacturing a Semiconductor Device)] The substrate processing method (method for manufacturing a semiconductor device) of this embodiment will be described below. Figure 12 is a flowchart illustrating an example of the overall process of the substrate processing method of the second embodiment of the present invention.

<SAM Formation Steps> In the SAM formation step S1' shown in Figure 12, the pretreatment step S101, the treatment solution preparation step S103, the membrane formation step S104, the removal step S105, and the drying step S106 are the same as in the first embodiment. Therefore, details of these steps are omitted.

1. Surface Modification Step ( Dry Method ) Surface modification step S102' is the same as surface modification step S102 in the first embodiment, and consists of the following steps: On the surface of the _SiO2 layer 1, areas where SAM molecules are difficult to chemically adsorb are modified into areas where SAM molecules can chemically adsorb. Furthermore, it is a step of surface modification 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 carried out by a dry method based on ultraviolet irradiation. In the case of ultraviolet irradiation, there are no particular limitations on the ultraviolet irradiation conditions, such as the wavelength, intensity, and duration of the light source, as long as the irradiation is sufficient to introduce hydroxyl groups to the surface of the _SiO2 layer 1 to the point where SAM molecules 5 can be chemically adsorbed. Furthermore, the ultraviolet irradiation is carried out, for example, in an atmosphere containing oxygen atoms, such as air.

<Etching Steps (Batch Process)> Etching step S2' is as follows: By immersing the SAM-formed substrate W in the etching solution, the SiN layer 2 to be etched is selectively etched.

As a method for immersing the substrate W in the etching solution, it is performed, for example, with the substrate W in an upright position. Here, "upright position" means that the surface of the substrate W is in a position that is generally vertical relative to the horizontal plane, including the case of a perpendicular position. As the etching solution, the same one described in the first embodiment can be used. Furthermore, the etching temperature (i.e., the temperature of the etching solution) and the etching rate of the etched layer can also be appropriately set, taking into account the constituent material of the etched layer, just as in the case of the first embodiment.

[Substrate Processing Apparatus (Semiconductor Manufacturing Apparatus)] Next, the substrate processing apparatus of this embodiment will be described below, taking its application in 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 has at least a monolithic substrate processing unit for forming SAM and a batch etching processing unit for etching the etched layer.

<Substrate Processing Unit> As shown in FIG13, the substrate processing unit 200 of this embodiment differs from the semiconductor manufacturing apparatus 100 of the first embodiment in that an ultraviolet irradiation unit 210 is provided as a surface modification unit instead of a surface modification liquid supply unit. FIG13 is an explanatory diagram showing the schematic structure of the substrate processing unit of this embodiment. In FIG13, some components common to the semiconductor manufacturing apparatus 100 of the first embodiment are omitted. Furthermore, in FIG13, the XYZ orthogonal coordinate axes are appropriately shown to clarify the directional relationship of the figures. Here, the XY plane represents the horizontal plane, and the +Z direction represents vertically upward.

The ultraviolet irradiation unit 210 is located inside the chamber 170 and is positioned above the substrate holding unit 110 in such a way that it can irradiate ultraviolet rays onto the surface Wf of the substrate W held by the substrate holding unit 110 (in the direction shown by arrow Z in FIG13). The ultraviolet irradiation unit 210 includes at least a plurality of light source units 211 and quartz glass 212.

The light source 211 shown in Figure 13 is a line light source, and its length direction is parallel to the direction shown by Y in Figure 13. Furthermore, each light source 211 is arranged at equal intervals in the direction shown by arrow X. However, the light source 211 of the present invention is not limited to this configuration. For example, it can also be a ring-shaped light source, and those with different diameters can be arranged in a concentric circle configuration. Furthermore, the light source can also be a point light source. In this case, it is preferable that a plurality of light sources are arranged at equal intervals in the plane.

There is no particular limitation on the type of light source unit 211. 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 type or different types. When multiple different types of light source units 211 are used, they can be configured to have different peak wavelengths or light intensities.

Quartz glass 212 is disposed between the light source unit 211 and the substrate W. Quartz glass 212 is plate-shaped and positioned parallel to the horizontal direction. Furthermore, quartz glass 212 is transparent to ultraviolet light, heat-resistant, and corrosion-resistant, allowing ultraviolet light irradiated from the light source unit 211 to pass through and irradiate the surface Wf of the substrate W. In addition, quartz glass 212 protects the light source unit 211 from the influence of the atmosphere within the chamber 170.

<Etching Processing Unit> The etching processing unit of this embodiment is a batch processing unit used to etch the etched layer. It performs etching step S2' on the substrate W with SAM formed in the substrate processing unit. As shown in Figures 14 and 15, the etching processing unit includes at least: a substrate transport section (not shown), a lift 220, and a processing tank 230 for storing etching solution. Figure 14 is a side view showing the schematic configuration of the lift 220 in the semiconductor manufacturing apparatus of this embodiment. Figure 15 is a cross-sectional view showing a plurality of substrates W with SAM formed in this embodiment immersed in etching solution.

The substrate transport unit transports the substrate W, on which SAM has been formed, from the substrate processing unit to the etching processing unit. The substrate transport unit may include, for example, a multi-joint robot capable of transporting the substrate W. The multi-joint robot has a transport arm at its front end capable of loading the substrate W in a horizontal position at one time.

As shown in FIG. 14, the lifting device 220 includes a flat back plate portion 221, a plurality of (3) retaining rods 222, and a lifting mechanism (not shown). The back plate portion 221 is vertically mounted, and at its lower end, the retaining rods 222 extend in one direction at right angles to the back plate portion 221. A plurality of grooves 223 are arranged on the retaining rods 222 in their extending direction. Furthermore, the plurality of grooves 223 are arranged at equal intervals. Moreover, each groove 223 extends in a direction at right angles to the extending direction of the retaining rods 222, and can fit into the plurality of substrates W in an upright posture. In this way, the retaining rods 222 can abut against the group of supporting substrates W from below in an upright posture and hold them together. Furthermore, there is no particular limitation on the number of retaining rods 222 if there is a plurality. Also, there is no particular limitation on the number of grooves 223 provided in the retaining rods 222, as long as they are appropriately set according to the number of substrates W to be retained. Furthermore, the lifting mechanism can raise or lower the lifting device 220 in the Z direction as shown in FIG. 15. This allows the lifting device 220, which holds a group of substrates W together, to move or be removed from inside the processing tank 230.

As shown in FIG. 15, the processing tank 230 includes: an injection pipe 231 for supplying etching solution into the processing tank 230, an inner tank 232 for storing etching solution, and an outer tank 233 located at the periphery of the upper opening of the inner tank 232. The injection pipe 231 is located at the bottom of the inner tank 232, enabling the upward flow of etching solution into the inner tank 232. Furthermore, the outer tank 233 can recover etching solution overflowing from the inner tank 232. The injection pipe 231 may also be connected, for example, to the etching solution storage unit 161 described in the first embodiment via a discharge pipe 169.

(Other Matters) The preferred embodiment of the present invention has been described above. However, the present invention is not limited to this embodiment. For example, in the first embodiment, the etching process of the SiN _2- layer is described as a monolithic process, but this etching process can also be performed in batches as described in the second embodiment. Furthermore, in the first embodiment, the surface modification process is described as a wet method, but this surface modification process can also be performed using the dry method based on ultraviolet irradiation as described in the second embodiment. Even in this isotropic sample, compared to previous film formation methods, SAM with higher film density and superior compactness can be formed on the substrate surface more efficiently in a shorter time, effectively suppressing or reducing the generation of film defects and providing excellent protection. [Example]

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

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

Next, the substrate, which was lifted from the hydrogen fluoride aqueous solution, was immersed in a surface modification solution for 10 minutes (surface modification step). As _the surface modification solution, SC-1 was used (by volume ratio, ammonium water ( _NH3 concentration 28%): hydrogen peroxide water ( _H2O2 concentration 30%): DIW = 1:4:20).

On the other hand, separate from the surface modification step of the substrate, a treatment solution is prepared. Specifically, 100 ppm of water is added to toluene, which serves as an organic solvent, in a sealed container at 23°C and atmospheric pressure. Then, the mixture containing toluene and water is subjected to ultrasound for 30 minutes while remaining stationary. This prepares a dispersion in toluene, the main solvent, in which water is uniformly dispersed. The ultrasound application conditions are set to a frequency of 45 Hz. Next, octadecyltrichlorosilane, used as a SAM forming material, is added to the stationary dispersion at 23°C and atmospheric pressure to prepare the treatment solution (treatment solution preparation step). The content (concentration) of octadecyltrichlorosilane relative to the total mass of the treatment fluid is set to 5 by mass.

Next, the substrate lifted from the surface modification solution is immersed in a treatment solution containing SAM forming material for 5 minutes to form SAM (approximately 1 nm thick) on the surface of the _SiO2 film on the substrate (film formation step).

Next, the substrate lifted from the treatment solution was immersed in toluene, which served as the removal solution, for 1 minute to remove the unadsorbed SAM forming material remaining on the surface of the substrate (removal step). Then, the substrate lifted from the toluene was dried by blowing nitrogen gas onto the surface where SAM was formed (drying step). The nitrogen temperature was set to room temperature, and the drying time was set to 1 minute.

Next, the dried substrate is immersed in DIW to remove toluene (rinsing step), and nitrogen gas is blown onto the surface with SAM to dry it (drying step). The nitrogen temperature is set to room temperature. In this way, a sample of this embodiment is produced.

Next, the obtained samples were subjected to etching. Specifically, the substrate was immersed in an etching solution, and the areas on the substrate surface not protected by SAM were etched. As etching conditions, the etching amount of _SiO2 was set to approximately 10 nm, and the immersion time in the etching solution (etching time) was set to 195 seconds. Furthermore, as the etching solution, an aqueous solution of hydrogen fluoride was used, and the volume ratio of hydrogen fluoride to DIW was set to hydrogen fluoride:DIW = 1:100.

Next, the substrate, which has been lifted from the etching solution, is immersed in the DIW (distillation water), and then lifted out of the DIW (using the rinsing step of the DIW). Nitrogen gas is then blown onto the etched surface to dry it (drying step). The temperature of the nitrogen gas is set to room temperature.

(Example 2) In this embodiment, the surface modification treatment of the substrate after the pretreatment step is changed to a method using ultraviolet irradiation. Otherwise, a sample is prepared in the same manner as in Example 1, and then the obtained sample is subjected to etching treatment.

Furthermore, the ultraviolet irradiation conditions are as follows: Light source for the ultraviolet irradiation unit: low-pressure mercury lamp (trade name: EUV200WS-51, manufactured by SEN Special Light Source Co., Ltd.) Peak wavelength of ultraviolet light: 185 nm, 254 nm Irradiation intensity of ultraviolet light: 10 mW/ ^cm² Irradiation time of ultraviolet light: 15 minutes Pressure inside the chamber: atmospheric pressure Temperature inside the chamber: 23℃ Atmosphere inside the chamber: air

(Comparative Example 1) In this comparative example, the water content in the treatment solution was changed to 300 ppm, and the surface modification treatment of the substrate after the pretreatment step was changed to an annealing process. Otherwise, a sample was prepared in the same manner as in Example 1, and the obtained sample was then subjected to etching.

Furthermore, the annealing process is set to a heating temperature of 600°C and a heating time of 30 minutes. After annealing, the substrate is allowed to cool naturally to room temperature.

(Comparative Example 2) In this comparative example, the heating temperature during annealing was changed to 300°C. Otherwise, samples were prepared in the same manner as in Comparative Example 1, and the resulting samples were then subjected to etching.

(Comparative Example 3) In this comparative example, no surface modification treatment was performed on the substrate after the pretreatment step. Otherwise, a sample was prepared in the same manner as in Example 1, and then the obtained sample was subjected to etching.

(Comparative Example 4) In this comparative example, instead of the surface modification solution containing SC-1, hydrochloric acid-hydrogen peroxide solution (SC-2) was used (by volume ratio, hydrochloric acid (concentration 36%): hydrogen peroxide (concentration 30-36%): DIW = 1:1:5). Otherwise, a sample was prepared in the same manner as in Example 1, and the obtained sample was then etched.

(Comparative Example 5) In this comparative example, nitric acid (by volume ratio, nitric acid:DIW = 1:3) was used instead of the surface modifier solution containing SC-1. Otherwise, a sample was prepared in the same manner as in Example 1, and the obtained sample was then etched.

(Evaluation of SiOH/Si) For the samples of Examples 1 and 2, and Comparative Examples 1-5, the SiOH/Si ratio was measured at two points using XPS analysis with a Quantera SXM (manufactured by PHI Corporation), and the average value was calculated. The results are shown in Table 1.

(SAM Density Evaluation) The area ratio (%) of film defects in the SAM was calculated for each sample of Examples 1 and 2, and Comparative Examples 1-5, to evaluate the density of the SAM.

That is, an atomic force microscope (AFM) (trade name: Dimension Icon, manufactured by Bruker Japan) is used to photograph the SAM of each sample, obtaining a 500 nm square observation image (AFM image). Then, after binarizing the obtained observation images, image processing is performed to map the film defects, thereby identifying the locations (regions) of film defects in the SAM. The specific mapping of the locations (regions) of film defects in the SAM is based on the fact that the SAM film thickness is approximately 1 nm; image processing is performed to map defects located less than 1 nm from the SAM surface. In this way, locations (regions) deeper than 1 nm from the SAM surface, and more specifically, etched areas, are mapped as SAM film defect regions, but are not included in their area. Next, for the areas of film defects in SAM identified by image processing, their areas were calculated, and the ratio of these areas to the total area in the observed image was calculated. The results are shown in Table 1.

(Results) As shown in Table 1, compared with Comparative Example 3, which did not undergo surface modification treatment, the SiOH/Si values of Example 1, which used SC-1 as the surface modification solution for surface modification, and Example 2, which underwent surface modification by ultraviolet irradiation, were all increased. On the other hand, compared with Comparative Example 3, the SiOH/Si values of Comparative Examples 1 and 2, which underwent surface modification by annealing treatment, Comparative Example 4, which underwent surface modification by using SPM as the surface modification solution, and Comparative Example 5, which underwent surface modification by using nitric acid as the surface modification solution, were not changed or decreased. Therefore, when surface modification was performed using SC-1 as a surface modification solution or by ultraviolet irradiation, it was confirmed that hydroxyl groups could be well imparted to the _SiO2 layer.

Furthermore, regarding the area ratio (%) of defects in the SAM film, Examples 1 and 2 were 10.7% and 10.0%, respectively, which were reduced compared to Comparative Example 3, which did not undergo surface modification treatment, or Comparative Examples 1, 2, 4, and 5, which underwent surface modification treatment by other methods. This confirms that the SAMs in Examples 1 and 2 both possess good density and protective properties.

[Table 1] Implementation Example 1 Implementation Example 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Surface modification method SC-1 UV irradiation Annealing (600℃) Annealing (300℃) - SPM Nitric acid SAM's density AFM Image Drawing Images Area ratio of membrane defects (%) 10.7 10.0 100 60.2 19.2 69.1 25.2 SiOH/Si No.1 0.085 0.095 0.062 0.070 0.074 0.072 0.068 No.2 0.080 0.087 0.059 0.066 0.072 0.074 0.069 average 0.0825 0.0910 0.0605 0.6800 0.0730 0.0730 0.0685

1: _SiO2 layer (protected layer) 2: SiN layer (etched layer) 3: Deposited layer 4: Storage trench 5: SAM (Autotonic Atomized Monomer) molecule 6: SAM (Autotonic Atomized Monomer) 7: Film defect 100: Semiconductor manufacturing apparatus 110: Substrate holding part 111: Rotating base 112: Rotating spindle 113: Rotating chuck 114: Suction cup rotation mechanism 115: Sleeve 116: Suction cup pin 120: Pretreatment solution supply part 121: Pretreatment solution storage part 122: Nozzle 123: Support arm 124: Pressurization part 124 a: Nitrogen supply source 124 b: Nitrogen supply pipe 124 c: Valve 125: Pretreatment liquid tank 125 a: Discharge pipe 125 b: Discharge valve 130: Surface modification liquid supply section 131: Surface modification liquid storage section 132: Nozzle 133: Support arm 134: Pressurization section 134 a: Nitrogen supply source 134 b: Nitrogen supply pipe 134 c: : Valve 135: Surface Modification Liquid Tank 135a: Discharge Pipe 135b: Discharge Valve 140: Treatment Liquid Supply Section 141: Treatment Liquid Storage Section 142: Nozzle 143: Support Arm 144: Organic Solvent Supply Section 144a: Organic Solvent Storage Section 144b: Organic Solvent Supply Pipe 144c: Valve 145: Water Supply Section 145a: Water storage section 145b: Water supply pipe 145c: Valve 146: SAM forming material supply section 146a: SAM forming material storage section 146b: SAM forming material supply pipe 146c: Valve 147: Treatment liquid tank 147a: Discharge pipe 147b: Discharge valve 148: Temperature adjustment section 149: Inert gas supply section 149a: Inert gas supply source 149b: Inert gas supply pipe 149c: Valve 150: Detergent supply section 151: Detergent storage section 152: Nozzle 153: Support arm 154: Pressurization section 154a: Nitrogen supply source 154b: Nitrogen supply pipe 154c: Valve 155: Detergent tank 155a: Discharge pipe 155b : Discharge valve 160: Etching solution supply unit 161: Etching solution storage unit 162: Nozzle 163: Support arm 164: Etching solution tank 165: Temperature regulator 166: Liquid pump 167: Particle filter 168: Mixer 169: Discharge pipe 170: Chamber 180: Anti-splash shield 190: Rotary drive unit 191: Ultrasonic application unit 200: Substrate processing unit 210: Ultraviolet irradiation unit 211: Light source unit 212: Quartz glass 220: Lifter 221: Back plate unit 222: Holding rod 223: Groove 230: Processing tank 231: Injection pipe 232: Inner tank 233: Outer tank 300: Control unit J1: Rotating shaft S1: SAM (Autotissue Monomer) Film Formation Step S1': SAM Formation Step S2: Etching Step S2': Etching Step S101: Pretreatment Step S102: Surface Modification Step S102': Surface Modification Step S103: Treatment Solution Preparation Step S104: Film Formation Step S105: Removal Step S106: Drying Step W: Substrate Wf: Surface of Substrate

Figure 1A is a schematic cross-sectional view of the laminate disposed on the substrate, showing the state before the etching step. Figure 1B is a schematic cross-sectional view of the laminate disposed on the substrate, showing the state after the etching step. Figure 2A is a partially enlarged view of the portion of the laminate in Figure 1A surrounded by A. Figure 2B is a partially enlarged view showing the formation of SAM on the surface of the _SiO2 layer. Figure 2C is a partially enlarged view of the portion of the laminate in Figure 1B surrounded by B, showing the SiN layer being etched. Figure 3 is a flowchart illustrating an example of the overall process of manufacturing a semiconductor device according to the first embodiment of the present invention. Figure 4A is a schematic diagram illustrating the surface state of the _SiO2 layer before surface modification in the first embodiment. Figure 4B is a schematic diagram illustrating the surface state of the _SiO2 layer after surface modification. Figure 4C is a schematic diagram illustrating the supply of treatment liquid to the surface of the _SiO2 layer. Figure 5A is a schematic diagram illustrating the chemical adsorption of SAM molecules on the surface of the _SiO2 layer. Figure 5B is a schematic diagram illustrating the self-organization of SAM molecules on the surface of the _SiO2 layer to form SAM. Figure 5C is an illustration illustrating the removal of SAM molecules remaining on the SAM. Figure 6 is a schematic diagram illustrating the schematic configuration of the semiconductor manufacturing apparatus of the first embodiment of the present invention. Figure 7 is a schematic diagram showing the pretreatment liquid storage section in the pretreatment liquid supply unit of the semiconductor manufacturing apparatus of the first embodiment of the present invention. Figure 8 is a schematic diagram showing the schematic diagram showing the surface modifier liquid storage section provided in the surface modifier liquid supply unit of the semiconductor manufacturing apparatus of the first embodiment of the present invention. Figure 9 is a schematic diagram showing the schematic diagram showing the processing liquid storage section and the ultrasonic application section in the processing liquid supply unit of the semiconductor manufacturing apparatus of the first embodiment of the present invention. Figure 10 is a schematic diagram showing the schematic diagram showing the removal liquid storage section provided in the removal liquid supply unit of the semiconductor manufacturing apparatus of the first embodiment of the present invention. Figure 11 is an explanatory diagram showing the schematic structure of the etching solution storage unit in the etching solution supply unit of the first embodiment of the present invention. Figure 12 is a flowchart showing an example of the overall process of the semiconductor device manufacturing method of the second embodiment of the present invention. Figure 13 is an explanatory diagram showing the schematic structure of the semiconductor manufacturing apparatus of the second embodiment of the present invention. Figure 14 is a side view showing the schematic structure of the elevator in the semiconductor manufacturing apparatus of the second embodiment of the present invention. Figure 15 is a cross-sectional view showing the case where a plurality of substrates with SAM formed are immersed in etching solution in the second embodiment of the present invention.

S1: SAM (Autologous Tissue Monolayer) Formation Steps

S2: Etching Steps

S101: Pretreatment Steps

S102: Surface modification steps

S103: Treatment Fluid Preparation Procedure

S104: Membrane formation steps

S105: Removal Steps

S106: Drying Steps

Claims (25)

A substrate processing method for forming a self-tissued monolayer on the surface of a substrate includes: a surface modification step, which involves applying hydroxyl groups to the surface of the substrate to modify its surface; a treatment solution preparation step, which involves adding a material capable of forming a self-tissued monolayer to a dispersion of water in an organic solvent to generate a treatment solution containing molecules capable of forming a self-tissued monolayer; and a film formation step, which involves contacting the treatment solution containing the molecules capable of forming the self-tissued monolayer with the surface of the substrate after the surface modification step to form the self-tissued monolayer; wherein the molecules have functional groups capable of undergoing dehydration condensation reactions with the hydroxyl groups. The above-mentioned film formation step is a step in which the above-mentioned molecules are chemically adsorbed onto the surface of the above-mentioned substrate by the dehydration condensation reaction of the above-mentioned hydroxyl group and the above-mentioned functional groups of the above-mentioned molecules. As in the substrate processing method of claim 1, the surface modification step is a step of contacting the surface modification liquid containing an alkaline solution with the surface of the substrate. As in the substrate processing method of claim 2, the alkaline solution is an ammonia-hydrogen peroxide mixture, ammonia water, tetramethylammonium hydroxide aqueous solution, or trimethyl-2-hydroxyethylammonium hydroxide aqueous solution. As in the substrate processing method of claim 1, the surface modification step is a step of irradiating the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms. The substrate processing method of claim 1 further includes a pretreatment step before the surface modification step, wherein the pretreatment step involves contacting the surface of the substrate with a pretreatment liquid containing hydrogen fluoride. As in the substrate processing method of claim 1, the substrate surface is provided with a _SiO2 layer, and the surface modification and the formation of the autotissue monolayer are performed on the _SiO2 layer. As in the substrate processing method of claim 1, the material capable of forming a self-tissued monolayer is a trichlorosilyl group. A method for manufacturing a semiconductor device includes processing a substrate having a laminate on its surface, the laminate comprising alternating layers of a protected layer and an etched layer, the manufacturing method comprising: selectively forming an autologous monolayer on at least the surface of the protected layer; and selectively etching the etched layer using the autologous monolayer as a protective layer, the step of forming the autologous monolayer comprising: a surface modification step, which involves applying hydroxyl groups to the surface of the protected layer to perform surface modification; and The membrane formation step involves contacting a treatment solution containing molecules capable of forming the aforementioned self-tissued monolayer with the surface of the protected layer after the surface modification step, thereby forming the aforementioned self-tissued monolayer. The molecules have functional groups capable of undergoing dehydration condensation reactions with the aforementioned hydroxyl groups. The membrane formation step is as follows: through the dehydration condensation reaction between the aforementioned hydroxyl groups and the aforementioned functional groups of the aforementioned molecules, the aforementioned molecules are chemically adsorbed onto the surface of the protected layer. As in the method of manufacturing a semiconductor device according to claim 8, the surface modification step is a step of contacting a surface modification liquid containing an alkaline solution with the surface of the protected layer. As in the method of manufacturing the semiconductor device of claim 9, the alkaline solution is an ammonia-hydrogen peroxide mixture, ammonia water, tetramethylammonium hydroxide aqueous solution, or trimethyl-2-hydroxyethylammonium hydroxide aqueous solution. As in the method of manufacturing a semiconductor device according to claim 8, the surface modification step is a step of irradiating the surface of the protected layer with ultraviolet light in an atmosphere containing oxygen atoms. The method of manufacturing a semiconductor device, as claimed in claim 8, further includes a pretreatment step prior to the surface modification step, wherein the pretreatment step involves contacting a pretreatment liquid containing hydrogen fluoride onto the surface of the protected layer. A substrate processing apparatus forms a self-tissued monolayer on the surface of a substrate and comprises: a surface modification section that applies hydroxyl groups to the surface of the substrate to perform surface modification; and a processing liquid supply section that adds a material capable of forming the self-tissued monolayer to a dispersion of water in an organic solvent to form a processing liquid, and supplies the processing liquid containing molecules capable of forming the self-tissued monolayer to the surface of the substrate surface modified by the surface modification section, thereby forming the self-tissued monolayer; wherein the molecules have functional groups capable of undergoing dehydration condensation reactions with the hydroxyl groups. The aforementioned processing liquid supply unit utilizes the dehydration condensation reaction between the aforementioned hydroxyl group and the aforementioned functional groups of the aforementioned molecule to chemically adsorb the aforementioned molecule onto the surface of the aforementioned substrate. As in the substrate processing apparatus of claim 13, the surface modification unit is a surface modification liquid supply unit that supplies a surface modification liquid containing an alkaline solution to the surface of the substrate. As in the substrate processing apparatus of claim 14, the alkaline solution is an ammonia-hydrogen peroxide mixture, ammonia, tetramethylammonium hydroxide aqueous solution, or trimethyl-2-hydroxyethylammonium hydroxide aqueous solution. As in claim 13, the substrate processing apparatus wherein the surface modification section is an ultraviolet irradiation section that irradiates the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms. The substrate processing apparatus of claim 13 further includes a pretreatment liquid supply unit, which supplies a pretreatment liquid containing hydrogen fluoride to the surface of the substrate before surface modification by the surface modification unit. As in the substrate processing apparatus of claim 13, a _SiO2 layer is provided on the surface of the substrate, and the surface modification and the formation of the autotissue monolayer are performed on the _SiO2 layer. As in the substrate processing apparatus of claim 13, the material capable of forming a self-tissued monolayer is a trichlorosilyl group. A semiconductor manufacturing apparatus performs processing on a substrate having a laminated body on its surface, the laminated body comprising alternating layers of a protected layer and an etched layer, the semiconductor manufacturing apparatus comprising: a surface modification section for applying hydroxyl groups to the surface of the protected layer to perform surface modification; and a processing liquid supply section for supplying a processing liquid containing molecules capable of forming a self-tissued monolayer to the surface of the protected layer after surface modification by the surface modification section, thereby forming the self-tissued monolayer; and The etching section uses the aforementioned autologous tissue monolayer as a protective layer to selectively etch and remove the etched layer; the aforementioned molecules have functional groups capable of undergoing dehydration condensation reactions with the aforementioned hydroxyl groups; the aforementioned processing liquid supply section chemically adsorbs the aforementioned molecules onto the surface of the protected layer through the dehydration condensation reaction between the aforementioned hydroxyl groups and the aforementioned functional groups possessed by the aforementioned molecules. A semiconductor manufacturing apparatus performs processing on a substrate having a laminated body on its surface, the laminated body comprising alternating layers of a protected layer and an etchable layer, the semiconductor manufacturing apparatus comprising: a substrate processing unit that selectively forms a self-tissued monolayer on at least the surface of the protected layer; and an etching processing unit that selectively etches and removes the etchable layer using the self-tissued monolayer as a protective layer; the substrate processing unit comprising: a surface modification section that performs surface modification by applying hydroxyl groups to the surface of the protected layer; and The treatment liquid supply unit supplies the surface of the protected layer, which has been surface-modified by the surface modification unit, with a treatment liquid containing molecules capable of forming the self-tissued monolayer, thereby forming the self-tissued monolayer. The molecules have functional groups capable of undergoing dehydration condensation reactions with the hydroxyl groups. The treatment liquid supply unit chemically adsorbs the molecules onto the surface of the protected layer through the dehydration condensation reaction between the hydroxyl groups and the functional groups of the molecules. The semiconductor manufacturing apparatus of claim 20 or 21, wherein the surface modification section is a surface modification liquid supply section that supplies a surface modification liquid containing an alkaline solution to the surface of the protected layer. As in the semiconductor manufacturing apparatus of claim 22, the alkaline solution is an ammonia-hydrogen peroxide mixture, ammonia, tetramethylammonium hydroxide aqueous solution, or trimethyl-2-hydroxyethylammonium hydroxide aqueous solution. The semiconductor manufacturing apparatus of claim 20 or 21, wherein the surface modification section is an ultraviolet irradiation section that irradiates the surface of the protected layer with ultraviolet light in an atmosphere containing oxygen atoms. The semiconductor manufacturing apparatus of claim 20 or 21 further includes a pretreatment liquid supply unit that supplies a pretreatment liquid containing hydrogen fluoride to the surface of the protected layer before surface modification by the surface modification unit.