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

Abstract

To provide: a substrate processing method and a substrate processing device, capable of forming a self-assembled monolayer on a substrate surface efficiently and in a short time, the self-assembled monolayer having excellent denseness and protection performance due to suppression or reduction in the occurrence of film defects; a method for manufacturing a semiconductor device; and a semiconductor manufacturing device.SOLUTION: A substrate processing method for forming a self-assembled monolayer (SAM) on a surface Wf of a substrate W. The substrate processing method includes: a surface modification step S102 for applying hydroxyl groups to the surface Wf of the substrate W to perform surface modification; and a film formation step S104 for bringing a treatment liquid containing SAM molecules capable of forming a SAM into contact with the surface Wf of the substrate W after the surface modification step S102 and thereby forming a SAM. The molecules have hydroxyl groups. The film formation step S104 includes chemically adsorbing the SAM molecules to the surface Wf of the substrate W using a dehydration condensation reaction between the hydroxyl groups applied to the surface Wf of the substrate W and the hydroxyl groups included in the SAM molecules, thereby forming a SAM.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present invention relates to a substrate processing method and substrate processing apparatus capable of efficiently forming a self-assembled monolayer having excellent density and protective performance in a short time, as well as a semiconductor device manufacturing method and semiconductor manufacturing apparatus. [Background technology]

[0002] In the manufacture of semiconductor devices, photolithography is widely used as a technique for selectively forming a film on a specific surface region of a substrate. For example, after forming a lower layer wiring, an insulating film is formed, and a dual damascene structure having trenches and via holes is formed by photolithography and etching, and a conductive film such as Cu is embedded in the trenches and via holes to form wiring.

[0003] However, in recent years, semiconductor devices have become increasingly miniaturized, and there are cases where the alignment accuracy of photolithography is insufficient. For this reason, there is a demand for an alternative to photolithography to selectively form a film in a specific region on the substrate surface with high accuracy.

[0004] 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 thermal phosphoric acid resistant material is formed as a SAM on the surface of the silicon oxide film in advance in order to selectively etch the silicon nitride film.

[0005] In order to adequately protect the silicon oxide film from the etching solution, it is necessary to form a highly dense SAM. However, with conventional SAM deposition methods, it is difficult to deposit such a highly dense SAM in a short time, resulting in poor production efficiency. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent No. 5490071 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in consideration of the above problems, and an object of the present invention is to provide a substrate processing method and substrate processing apparatus, as well as a semiconductor device manufacturing method and semiconductor manufacturing apparatus, which are capable of efficiently forming a self-assembled monolayer having excellent density and protective performance on a substrate surface in a short time by suppressing or reducing the occurrence of film defects. [Means for solving the problem]

[0008] In order to solve the above-mentioned problems, the substrate processing method of the present invention is a substrate processing method for forming a self-assembled monolayer on a surface of a substrate, comprising: a surface modification step of modifying the surface of the substrate by adding hydroxyl groups to the surface of the substrate; and a film formation step of contacting the surface of the substrate after the surface modification step with a treatment liquid containing molecules capable of forming the self-assembled monolayer to form the self-assembled monolayer, wherein the molecules have functional groups capable of undergoing a dehydration condensation reaction with the hydroxyl groups, and the film formation step is a step of chemically adsorbing the molecules onto the surface of the substrate by a dehydration condensation reaction between the hydroxyl groups and the functional groups possessed by the molecules.

[0009] In the film formation step in the above-mentioned configuration, a self-assembled monolayer (hereinafter, sometimes referred to as "SAM") is formed by chemically adsorbing molecules (hereinafter, sometimes referred to as "SAM molecules") capable of forming a SAM on the surface of a substrate and self-organizing the SAM. Here, in the SAM formed in the film formation step, the SAM molecules may not be able to be locally chemically adsorbed on the surface of the substrate, resulting in film defects. In particular, when the contact time of the SAM molecules with the substrate surface is short, the frequency of film defects in the surface increases, or the area of ​​the film defects becomes large. However, in the above-mentioned configuration, a surface modification step of adding hydroxyl groups to the substrate surface is performed before the film formation step. Therefore, when the SAM molecules having functional groups capable of dehydration condensation reaction with hydroxyl groups 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, and the SAM molecules can be chemically adsorbed on the substrate surface at a high density. As a result, unlike conventional substrate processing methods, the formation of a dense SAM does not require long periods of contact of SAM molecules with the substrate surface. Instead, the occurrence of film defects can be suppressed, and a SAM with excellent density and protective performance can be efficiently formed in a short period of time.

[0010] In the above configuration, the surface modification step may be a step of contacting the surface of the substrate with a surface modification liquid made of an alkaline solution. By contacting the surface of the substrate with the alkaline solution, 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, and a SAM with excellent density and protective performance can be formed.

[0011] Furthermore, in the above-mentioned configuration, the alkaline solution is preferably an ammonia-hydrogen peroxide solution mixture, ammonia water, a tetramethylammonium hydroxide aqueous solution, or a trimethyl-2-hydroxyethylammonium hydroxide aqueous solution.

[0012] In the above-mentioned configuration, the surface modification step may be a step of irradiating the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms. This allows more hydroxyl groups to be added to the surface of the substrate. As a result, more SAM molecules can be chemically adsorbed onto the surface of the substrate, and a SAM with excellent density and protective performance can be formed.

[0013] In the above-mentioned configuration, it is preferable to further include a pretreatment step of contacting the surface of the substrate with a pretreatment liquid containing hydrogen fluoride before the surface modification step. This allows the introduction of hydroxyl groups in the surface modification step to be performed well. As a result, the SAM molecules can be chemically adsorbed on the surface of the substrate with a higher density, and a SAM with even better density and protective performance can be formed.

[0014] In order to solve the above-mentioned problems, the manufacturing method of the present invention is a manufacturing method of a semiconductor device including processing a substrate having a laminate on its surface, the laminate including an alternately stacked protected layer to be protected during etching and an etched layer to be etched, the method including a step of selectively forming a self-assembled monolayer on at least a surface of the protected layer, and a step of selectively etching the etched layer using the self-assembled monolayer as a protective layer, the step of forming the self-assembled monolayer including a surface modification step of modifying the surface of the protected layer by adding a hydroxyl group, and a film formation step of contacting the surface of the protected layer after the surface modification step with a treatment liquid including molecules capable of forming the self-assembled monolayer to form the self-assembled monolayer, the molecules having functional groups capable of undergoing a dehydration condensation reaction with the hydroxyl groups, and the film formation step being a step of chemically adsorbing the molecules onto the surface of the protected layer by a dehydration condensation reaction between the hydroxyl groups and the functional groups possessed by the molecules.

[0015] In the film formation step in the above configuration, the SAM is formed by chemically adsorbing the SAM molecules to the surface of the layer to be protected and self-organizing it. Here, in the SAM formed in the film formation step, the SAM molecules may not be able to chemically adsorb locally to the surface of the layer to be protected, and film defects may occur. In particular, when the contact time of the SAM molecules with the surface of the layer to be protected is short, the frequency of film defects occurring in the plane increases, and the area of ​​the film defects becomes large. However, in the above configuration, before the film formation step, a surface modification step is performed to impart hydroxyl groups to the surface of the layer to be protected. Therefore, when the SAM molecules having functional groups capable of dehydration condensation reaction with hydroxyl groups contact the surface of the layer to be protected, a dehydration condensation reaction occurs between the functional groups of the SAM molecules and the hydroxyl groups on the surface of the layer to be protected, and the SAM molecules can be chemically adsorbed to the surface of the layer to be protected at a high density. As a result, even if the SAM molecules are not kept in contact with the surface of the layer to be protected for a long time in order to form a dense SAM, as in the conventional semiconductor device manufacturing method, the occurrence of film defects can be suppressed, and a SAM with excellent density and protection performance can be efficiently formed in a short time.

[0016] In the above-mentioned configuration, the surface modification step may be a step of contacting the surface of the layer to be protected with a surface modification liquid made of an alkaline solution. By contacting the surface of the layer to be protected with the alkaline solution, more hydroxyl groups can be imparted to the surface of the layer to be protected. As a result, more SAM molecules can be chemically adsorbed to the surface of the layer to be protected, and a SAM with excellent density and protection performance can be formed.

[0017] Furthermore, in the above-mentioned configuration, the alkaline solution is preferably an ammonia-hydrogen peroxide solution mixture, ammonia water, a tetramethylammonium hydroxide aqueous solution, or a trimethyl-2-hydroxyethylammonium hydroxide aqueous solution.

[0018] In the above-mentioned configuration, the surface modification step may be a step of irradiating the surface of the layer to be protected with ultraviolet light in an atmosphere containing oxygen atoms. This allows more hydroxyl groups to be added to the surface of the layer to be protected. As a result, more SAM molecules can be chemically adsorbed onto the surface of the layer to be protected, and a SAM with excellent density and protection performance can be formed.

[0019] In the above-mentioned configuration, it is preferable to further include a pretreatment step of contacting the surface of the layer to be protected with a pretreatment liquid containing hydrogen fluoride before the surface modification step. This allows the introduction of hydroxyl groups in the surface modification step to be performed well. As a result, the SAM molecules can be chemically adsorbed on the surface of the layer to be protected with a higher density, and a SAM with even better density and protection performance can be formed.

[0020] In order to solve the above-mentioned problems, the substrate processing apparatus of the present invention is a substrate processing apparatus that forms a self-assembled monolayer on a surface of a substrate, and includes a surface modification unit that performs surface modification by adding hydroxyl groups to the surface of the substrate, and a processing liquid supply unit that forms the self-assembled monolayer by supplying a processing liquid containing molecules capable of forming the self-assembled monolayer to the surface of the substrate that has been surface-modified by the surface modification unit, the molecules having functional groups capable of undergoing a dehydration condensation reaction with the hydroxyl groups, and the processing liquid supply unit chemically adsorbs the molecules to the surface of the substrate by a dehydration condensation reaction between the hydroxyl groups and the functional groups possessed by the molecules.

[0021] According to the above-mentioned configuration, the surface modification unit modifies the surface of the substrate by adding hydroxyl groups to the surface of the substrate. The processing liquid supply unit forms a SAM by contacting the surface of the substrate with a processing liquid containing SAM molecules. Here, since the SAM molecules have functional groups capable of dehydration condensation reaction with hydroxyl groups, when the 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, and the SAM molecules can be chemically adsorbed to the substrate surface. Furthermore, the chemically adsorbed SAM molecules self-assemble, thereby forming a SAM. Here, in the SAM formed on the substrate surface, the SAM molecules may not be able to be chemically adsorbed to the substrate surface locally, and film defects may occur. In particular, when the contact time of the SAM molecules with the substrate surface is short, the frequency of film defects in the surface increases, or the area of ​​the film defects becomes large. However, the above-mentioned configuration further includes a surface modification unit that modifies the surface of the substrate before the formation of the SAM. More specifically, the surface modification unit that adds hydroxyl groups to the substrate surface is provided. As a result, with the above configuration, the area where the SAM molecules cannot be chemically adsorbed is reduced, and even without having to keep the SAM molecules in contact with the substrate surface for a long period of time as in conventional substrate processing apparatuses to form a dense SAM, the occurrence of film defects can be suppressed, and a SAM with excellent density and protective performance can be efficiently formed in a short period of time.

[0022] In the above configuration, the surface modification unit may be a surface modification liquid supply unit that supplies a surface modification liquid made of an alkaline solution to the surface of the substrate. By supplying the surface modification liquid made of an alkaline solution to the substrate surface by the surface modification liquid supply unit, hydroxyl groups can be imparted to the surface of the substrate. This can minimize the area where SAM molecules cannot be chemically adsorbed, and more SAM molecules can be chemically adsorbed to the substrate surface at a high density. As a result, a SAM with excellent density and protective performance can be formed.

[0023] Furthermore, in the above-mentioned configuration, the alkaline solution is preferably an ammonia-hydrogen peroxide solution mixture, ammonia water, a tetramethylammonium hydroxide aqueous solution, or a trimethyl-2-hydroxyethylammonium hydroxide aqueous solution.

[0024] In the above configuration, the surface modification unit may be an ultraviolet irradiation unit that irradiates the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms. By irradiating the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms, the ultraviolet irradiation unit can impart hydroxyl groups to the surface of the substrate. This can minimize the area where SAM molecules cannot be chemically adsorbed, and more SAM molecules can be chemically adsorbed to the surface of the substrate at a high density. As a result, a SAM with excellent density and protective performance can be formed.

[0025] In the above configuration, it is preferable to further include a pretreatment liquid supply unit that supplies a pretreatment liquid containing hydrogen fluoride to the surface of the substrate before the surface is modified by the surface modification unit. The pretreatment liquid supply unit supplies a pretreatment liquid containing hydrogen fluoride to the substrate surface before the surface is modified, so that hydroxyl groups can be introduced well when the surface is modified by the surface modification unit. As a result, the SAM molecules can be chemically adsorbed to the substrate surface at a higher density, and a SAM with even better density and protective performance can be formed.

[0026] In order to solve the above-mentioned problems, the semiconductor manufacturing apparatus of the present invention is a semiconductor manufacturing apparatus that processes a substrate having a laminate provided on its surface, the laminate including an alternating layer of a protected layer to be protected by etching and an etched layer to be etched, the apparatus including a surface modification unit that performs surface modification by adding hydroxyl groups to the surface of the protected layer, a processing liquid supply unit that forms the self-assembled monolayer by supplying a processing liquid including molecules capable of forming a self-assembled monolayer to the surface of the protected layer that has been surface-modified by the surface modification unit, and an etching unit that selectively etches and removes the etched layer using the self-assembled monolayer as a protective layer, the molecules having functional groups capable of a dehydration condensation reaction with the hydroxyl groups, and the processing liquid supply unit chemically adsorbs the molecules to the surface of the protected layer by a dehydration condensation reaction between the hydroxyl groups and the functional groups of the molecules.

[0027] The semiconductor manufacturing apparatus of the above configuration forms a SAM on at least the surface of the layer to be protected before etching the layer to be etched, thereby enabling excellent selective etching of the layer to be etched. In the above configuration, the surface modification unit applies hydroxyl groups to the surface of the layer to be protected, thereby modifying the surface. The processing liquid supply unit forms a SAM by contacting the surface of the layer to be protected with a processing liquid containing SAM molecules. Here, since the SAM molecule has a functional group capable of dehydration condensation reaction with hydroxyl groups, when the SAM molecule contacts the surface of the layer to be protected, a dehydration condensation reaction occurs between the functional group of the SAM molecule and the hydroxyl group on the surface of the layer to be protected, and the SAM molecule can be chemically adsorbed. Furthermore, the chemically adsorbed SAM molecule self-organizes, thereby forming a SAM. Here, in the SAM formed on the surface of the layer to be protected, the SAM molecule may not be able to be chemically adsorbed locally on the surface of the layer to be protected, and film defects may occur. In particular, when the contact time of the SAM molecule with the surface of the layer to be protected is short, the frequency of film defects in the surface increases, or the area of ​​the film defects becomes large. However, the above-mentioned configuration further includes a surface modification unit that performs surface modification on the surface of the layer to be protected before the formation of the SAM. More specifically, the surface modification unit provides a hydroxyl group on the surface of the layer to be protected. As a result, the above-mentioned configuration reduces the area where the SAM molecules cannot be chemically adsorbed, and unlike conventional semiconductor manufacturing devices, it is not necessary to keep the SAM molecules in contact with the surface of the layer to be protected for a long period of time to form a dense SAM. This makes it possible to suppress the occurrence of film defects and efficiently form a SAM with excellent denseness and protective performance in a short period of time.

[0028] In order to solve the above-mentioned problems, the semiconductor manufacturing apparatus of the present invention is a semiconductor manufacturing apparatus that processes a substrate having a laminate provided on its surface, the laminate including an alternately stacked protected layer that is to be protected by etching and an etched layer that is to be etched, the apparatus comprising: a substrate processing unit that selectively forms a self-assembled monolayer on at least the surface of the protected layer; and an etching processing unit that selectively etches and removes the etched layer using the self-assembled monolayer as a protective layer, the substrate processing unit comprising: a surface modification section that performs surface modification by adding hydroxyl groups to the surface of the protected layer; and a processing liquid supply section that forms the self-assembled monolayer by supplying a processing liquid containing molecules capable of forming the self-assembled monolayer to the surface of the protected layer that has been surface-modified by the surface modification section, the molecules having functional groups capable of undergoing a dehydration condensation reaction with the hydroxyl groups, and the processing liquid supply section chemically adsorbs the molecules to the surface of the protected layer by a dehydration condensation reaction between the hydroxyl groups and the functional groups of the molecules.

[0029] The semiconductor manufacturing apparatus of the above configuration includes at least a substrate processing unit that selectively forms a SAM on the layer to be protected, and an etching processing unit that selectively etches and removes the layer to be etched. Before etching the layer to be etched in the etching processing unit, the substrate processing unit forms a SAM on at least the surface of the layer to be protected to protect the layer to be etched, thereby enabling excellent selective etching of the layer to be etched. In the above configuration, the surface modification unit applies hydroxyl groups to the surface of the layer to be protected, thereby modifying the surface. In addition, the processing liquid supply unit forms a SAM by contacting the surface of the layer to be protected with a processing liquid containing SAM molecules. Here, since the SAM molecule has a functional group capable of dehydration condensation reaction with hydroxyl groups, when the SAM molecule contacts the surface of the layer to be protected, a dehydration condensation reaction occurs between the functional group of the SAM molecule and the hydroxyl group on the surface of the layer to be protected, and the SAM molecule can be chemically adsorbed. Furthermore, the chemically adsorbed SAM molecule self-organizes, thereby forming a SAM. Here, in the SAM formed on the surface of the layer to be protected, the SAM molecule may not be able to be chemically adsorbed locally on the surface of the layer to be protected, resulting in film defects. In particular, when the contact time of the SAM molecules with the surface of the layer to be protected is short, the frequency of occurrence of film defects in the surface increases, or the area of ​​film defects becomes large. However, the above-mentioned configuration further includes a surface modification unit that performs surface modification of the surface of the layer to be protected before the formation of the SAM. More specifically, the surface modification unit that imparts hydroxyl groups to the surface of the layer to be protected is provided. As a result, the above-mentioned configuration reduces the area where the SAM molecules cannot be chemically adsorbed, and the occurrence of film defects can be suppressed and a SAM with excellent density and protective performance can be efficiently formed in a short time without having to keep the SAM molecules in contact with the surface of the layer to be protected for a long time to form a dense SAM, as in conventional semiconductor manufacturing equipment.

[0030] In the above configuration, the surface modification unit may be a surface modification liquid supply unit that supplies a surface modification liquid made of an alkaline solution to the surface of the layer to be protected. By the surface modification liquid supply unit supplying the surface modification liquid made of an alkaline solution to the surface of the layer to be protected, hydroxyl groups can be imparted to the surface of the layer to be protected. This makes it possible to minimize the area where SAM molecules cannot be chemically adsorbed, and to allow more SAM molecules to be chemically adsorbed to the surface of the layer to be protected at a high density. As a result, a SAM with excellent density and protective performance can be formed.

[0031] Furthermore, in the above-mentioned configuration, the alkaline solution is preferably an ammonia-hydrogen peroxide solution mixture, ammonia water, a tetramethylammonium hydroxide aqueous solution, or a trimethyl-2-hydroxyethylammonium hydroxide aqueous solution.

[0032] In the above configuration, the surface modification unit may be an ultraviolet irradiation unit that irradiates the surface of the protected layer with ultraviolet light in an atmosphere containing oxygen atoms. By irradiating the surface of the protected layer with ultraviolet light in an atmosphere containing oxygen atoms, the ultraviolet irradiation unit can impart hydroxyl groups to the surface of the protected layer. This can minimize the area where SAM molecules cannot be chemically adsorbed, and more SAM molecules can be chemically adsorbed to the surface of the protected layer at a high density. As a result, a SAM with excellent density and protective performance can be formed.

[0033] In the above configuration, it is preferable to further include a pretreatment liquid supply unit that supplies a pretreatment liquid containing hydrogen fluoride to the surface of the layer to be protected before the surface is modified by the surface modification unit. By the pretreatment liquid supply unit supplying a pretreatment liquid containing hydrogen fluoride to the surface of the layer to be protected before the surface is modified, the introduction of hydroxyl groups can be performed well when the surface is modified by the surface modification unit. As a result, the SAM molecules can be chemically adsorbed to the surface of the layer to be protected with even higher density, and a SAM with even better density and protective performance can be formed. Effect of the Invention

[0034] According to the present invention, it is possible to provide a substrate processing method and substrate processing apparatus, as well as a semiconductor device manufacturing method and semiconductor manufacturing apparatus, which are capable of effectively suppressing or reducing the occurrence of film defects and efficiently forming a self-assembled monolayer having high film density and excellent compactness and protective performance on a substrate surface in a shorter time than conventional methods. [Brief description of the drawings]

[0035] [Figure 1] 1A and 1B are cross-sectional views each showing a schematic representation of a laminate provided on a substrate, in which FIG. 1A shows the state before an etching step, and FIG. 1B shows the state after the etching step. [Diagram 2] FIG. 2(a) is a partial enlarged view of the portion surrounded by A in the laminate in FIG. 1(a), FIG. 2(b) is a partial enlarged view showing the formation of a SAM on the surface of the SiO2 layer, and FIG. 2(c) is a partial enlarged view of the portion surrounded by B in the laminate in FIG. 1(b), showing the etching of the SiN layer. [Diagram 3] 3 is a flowchart showing an example of an overall flow of a method for manufacturing a semiconductor device according to a first embodiment of the present invention. [Figure 4] FIG. 4(a) is an explanatory diagram conceptually showing the surface state of the SiO2 layer before surface modification in the first embodiment, FIG. 4(b) is an explanatory diagram conceptually showing the surface state of the SiO2 layer after surface modification, and FIG. 4(c) is an explanatory diagram showing the state in which a treatment liquid is supplied to the surface of the SiO2 layer. [Diagram 5] Figure 5(a) is an explanatory diagram showing how the SAM molecules are chemically adsorbed onto the surface of the SiO2 layer, Figure 5(b) is an explanatory diagram showing how the SAM molecules self-organize on the surface of the SiO2 layer to form a SAM, and Figure 5(c) is an explanatory diagram showing how the SAM molecules remaining on the SAM are removed. [Figure 6] 1 is an explanatory diagram illustrating a schematic configuration of a semiconductor manufacturing apparatus according to a first embodiment of the present invention. [Figure 7] 1 is an explanatory diagram illustrating a schematic configuration of a pre-treatment liquid storage unit in a pre-treatment liquid supply unit in a semiconductor manufacturing apparatus according to a first embodiment of the present invention. FIG. [Figure 8]1 is an explanatory diagram illustrating a schematic configuration of a surface modification liquid storage unit provided in a surface modification liquid supply unit in a semiconductor manufacturing apparatus according to a first embodiment of the present invention. FIG. [Figure 9] 1 is an explanatory diagram illustrating a schematic configuration of a processing liquid storage unit and an ultrasonic wave application unit in a processing liquid supply unit in a semiconductor manufacturing apparatus according to a first embodiment of the present invention. [Figure 10] 2 is an explanatory diagram illustrating a schematic configuration of a removing liquid reservoir provided in a removing liquid supply unit in the semiconductor manufacturing apparatus according to the first embodiment of the present invention. FIG. [Figure 11] FIG. 2 is an explanatory diagram illustrating a schematic configuration of an etching liquid storage section in an etching liquid supply section in the first embodiment of the present invention. [Figure 12] 10 is a flowchart showing an example of an overall flow of a method for manufacturing a semiconductor device according to a second embodiment of the present invention. [Figure 13] FIG. 11 is an explanatory diagram illustrating a schematic configuration of a semiconductor manufacturing apparatus according to a second embodiment of the present invention. [Figure 14] 11 is a side view showing a schematic configuration of a lifter in a semiconductor manufacturing apparatus according to a second embodiment of the present invention. FIG. [Figure 15] FIG. 11 is a cross-sectional view showing a state in which a plurality of substrates on which a SAM is formed are immersed in an etching solution in a second embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0036] (First embodiment) A first embodiment of the present invention will be described below.

[0037] [Substrate Processing Method (Semiconductor Device Manufacturing Method)] First, a substrate processing method according to the present embodiment will be described below with reference to the drawings. The substrate processing method of the present embodiment provides a technique for enabling good selective etching when forming a three-dimensional structure, such as a three-dimensional NAND structure, on the surface of a substrate.

[0038] The substrate processing method of this embodiment is applicable to a part of the process of forming a three-dimensional NAND structure on a substrate W made of silicon or the like. Therefore, hereinafter, an example in which the substrate processing method of this embodiment is applied to a method of manufacturing a semiconductor device will be described. More specifically, a case where processing is performed on a substrate W provided with a laminate 3 having a three-dimensional structure as shown in FIG. 1 will be taken as an example. FIG. 1 is a cross-sectional view schematically showing the laminate provided on the substrate W, where FIG. 1(a) shows the state before the etching process, and FIG. 1(b) shows the state after the etching process.

[0039] As shown in FIG. 2(a), the laminate 3 includes a structure in which an SiO2 layer 1 functioning as an interlayer insulating layer and a SiN layer 2 functioning as a sacrificial layer are alternately laminated on the substrate W. In addition, the laminate 3 is provided with a plurality of memory trenches 4 extending so as to penetrate the laminate 3 in a direction perpendicular to the surface of the substrate W. Note that FIG. 2(a) is a partial enlarged view of the portion surrounded by A in the laminate of FIG. 1(a).

[0040] As shown in FIG. 3, the method of manufacturing a semiconductor device according to this embodiment includes at least a self-assembled monolayer (hereinafter referred to as "SAM") formation step S1 and an etching step S2, and enables the SiN layer 2 to be selectively etched through the memory trench 4 to form a recess on the side surface of the memory trench 4 in the laminate 3. FIG. 3 is a flowchart showing an example of the overall flow of the method of manufacturing a semiconductor device according to this embodiment.

[0041] <SAM formation step> The SAM formation step S1 is a step of selectively forming a SAM as a protective layer on the surface of the SiO2 layer 1 as a layer to be protected. As shown in FIG. 3, the SAM formation step S1 includes at least a pretreatment step S101, a surface modification step S102, a treatment liquid preparation step S103, a film formation step S104, a removal step S105, and a drying step S106. Note that the SAM formation step S1 corresponds to the substrate processing method of the present invention.

[0042] 1.Pretreatment process The pretreatment step S101 is a step of removing organic molecules that are physically adsorbed on the surface of the SiO2 layer 1, which is the layer to be protected, and cover the surface of the SiO2 layer 1 in the form of particles or a thin film. This step is optional, but it is preferable to perform this step from the viewpoint of improving the surface modification of the substrate W in the surface modification step S102 described later. Specifically, the pretreatment step S101 is performed by bringing a pretreatment liquid into contact with the surface of the substrate W.

[0043] The method for contacting the pretreatment liquid with the substrate W is not particularly limited, and examples thereof include a method of applying the pretreatment liquid to the surface of the substrate W, a method of spraying the pretreatment liquid onto the surface of the substrate W, and a method of immersing the substrate W in the pretreatment liquid.

[0044] An example of a method for applying the pretreatment liquid to the surface of the substrate W is to supply the pretreatment liquid to the center of the surface of the substrate W while rotating the substrate W at a constant speed around its center as an axis. In this way, the pretreatment liquid supplied to the surface of the substrate W flows from near the center of the surface of the substrate W toward the peripheral edge of the substrate W due to centrifugal force generated by the rotation of the substrate W, and is spread over the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered with the pretreatment liquid, and a liquid film of the pretreatment liquid is formed.

[0045] The conditions for contacting the substrate W with the pretreatment liquid are not particularly limited, but the time for which the substrate W is contacted with the pretreatment liquid (when the substrate W is immersed in the pretreatment liquid, the immersion time) is not particularly limited and can be set appropriately. However, by setting the contact time of the pretreatment liquid to 1 minute or less, it is possible to prevent the surface portion of the SiO2 layer from being excessively etched.

[0046] The temperature of the pretreatment liquid is not particularly limited and can be set as necessary, for example, to room temperature, etc. In this specification, "room temperature" means a temperature range of 5°C to 35°C.

[0047] The pretreatment liquid is not particularly limited, and examples thereof include hydrofluoric acid (for example, a volume ratio of HF:deionized water (DIW)=1:100).

[0048] 2. Surface modification process (wet method) The surface modification step S102 is a step of modifying the surface of the SiO2 layer 1 shown in Fig. 4(a) to change an area where SAM molecules are difficult to chemisorb into an area where SAM molecules can be chemisorbed. Also, in the area where SAM molecules can be chemisorbed, it is a step of enabling SAM molecules to be chemisorbed at a higher density. Fig. 4(a) is an explanatory diagram conceptually showing the surface state of the SiO2 layer 1 before the surface modification.

[0049] When the surface of the SiO2 layer 1 is modified in the surface modification step S102, hydroxyl groups that enable chemical adsorption of SAM molecules are provided to the surface, as shown in Fig. 4(b). Fig. 4(b) is an explanatory diagram conceptually showing the surface state of the SiO2 layer 1 after the surface modification.

[0050] In this embodiment, the surface of the SiO2 layer 1 is modified by a wet method. More specifically, the surface is modified by bringing a surface modification liquid into contact with the surface of the substrate W after the pretreatment step S101. The method of bringing the surface modification liquid into contact with the surface of the substrate W is not particularly limited, and examples thereof include a method of applying the surface modification liquid to the surface of the substrate W, a method of spraying the surface modification liquid onto the surface of the substrate W, and a method of immersing the substrate W in the surface modification liquid.

[0051] Further, as a method of applying the surface modification liquid to the surface of the substrate W, for example, there is a method in which the surface modification 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 center as an axis. In this way, the surface modification liquid supplied to the surface of the substrate W flows from near the center of the surface of the substrate W toward the peripheral edge of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and is spread over the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered with the surface modification liquid, and a liquid film of the surface modification liquid is formed.

[0052] The surface modification liquid is not particularly limited as long as it can provide hydroxyl groups to the surface of the SiO2 layer 1. Specific examples of the surface modification liquid include an ammonia-hydrogen peroxide solution mixture (Standard Clean-1 (SC-1)) (volume ratio of ammonium water (NH3 concentration 28%): hydrogen peroxide solution (H2O2 concentration 30%): DIW = 1:4:20), ammonia water, a tetramethylammonium hydroxide aqueous solution, and a trimethyl-2-hydroxyethylammonium hydroxide aqueous solution. Among these alkaline solutions, an ammonia-hydrogen peroxide solution mixture is preferable from the viewpoint of providing hydroxyl groups well to the SiO2 layer.

[0053] The conditions for contacting the substrate W with the surface modification liquid are not particularly limited, but the time for contacting the substrate W with the surface modification liquid (when the substrate W is immersed in the surface modification liquid, the immersion time) is not particularly limited and can be set appropriately. However, by making the contact time of the surface modification liquid 10 minutes or more, it is possible to provide sufficient hydroxyl groups to the surface of the SiO2 layer 1. This reduces the area where molecules capable of forming a SAM (hereinafter sometimes referred to as "SAM molecules") cannot be chemically adsorbed, and the SAM molecules can be chemically adsorbed at a high density on the surface of the SiO2 layer 1. As a result, the occurrence of film defects is suppressed, and a SAM with excellent density and protective performance can be efficiently formed in a short time.

[0054] The temperature of the surface modifying liquid is not particularly limited, and can be set as appropriate as necessary, for example, to room temperature.

[0055] In addition, when the surface modification step S102 is performed by a wet method, a cleaning step for removing the surface modification liquid and a drying step may be performed in sequence immediately after the surface modification step S102. The cleaning method in the cleaning step is not particularly limited, and examples thereof include a method of supplying a cleaning liquid to the surface of the substrate W and a method of immersing the substrate W in the cleaning liquid. Examples of the cleaning liquid include toluene, decane, and 1,3-bis(trifluoromethyl)benzene. These solvents can be used alone or in a mixture of two or more. The cleaning conditions such as the cleaning time and the temperature of the cleaning liquid are not particularly limited, and can be set appropriately as needed. The drying step is intended to remove the cleaning liquid remaining on the surface of the substrate W. The drying method is not particularly limited, and examples thereof include a method of spraying an inert gas such as nitrogen gas onto the surface of the substrate W. The drying conditions such as the drying time and the drying temperature are not particularly limited, and can be set appropriately as needed.

[0056] 3. Processing solution preparation process The treatment liquid preparation step S103 is a step of generating a treatment liquid containing SAM molecules. The treatment liquid is used to form a SAM on the surface of the SiO2 layer 1, which is the layer to be protected. The treatment liquid is prepared, for example, as follows.

[0057] First, a dispersion liquid in which water is uniformly dispersed in an organic solvent as a main solvent is prepared. The term "water is uniformly dispersed in an organic solvent" means, for example, that water is present in the organic solvent in the form of an emulsion. The term "main solvent" means the solvent with the largest volume ratio when a mixed solvent consisting of multiple solvents is used.

[0058] Examples of the organic solvent that is the main solvent include ether solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, fluorine solvents, and ketone solvents. The ether solvent is not particularly limited, and examples thereof include tetrahydrofuran (THF). The aromatic hydrocarbon solvent is not particularly limited, and examples thereof include toluene. The aliphatic hydrocarbon solvent is not particularly limited, and examples thereof include decane. The fluorine solvent is not particularly limited, and examples thereof include 1,3-bis(trifluoromethyl)benzene. The ketone solvent is not particularly limited, and examples thereof include methyl ethyl ketone. These solvents can be used alone or in combination of two or more. Among the solvents exemplified above, aromatic hydrocarbon solvents are preferred from the viewpoint of affinity with water, and toluene is particularly preferred. In addition, the organic solvent that is the main solvent is preferably one that has a low solubility of water. This allows water to be well dispersed in the organic solvent. Examples of the organic solvent that has a low solubility of water include the above-mentioned toluene.

[0059] The amount of water added in the dispersion is preferably in the range of 50 ppm or more and 200 ppm or less, and more preferably in the range of 50 ppm or more and 150 ppm or less. By making the amount of water added 50 ppm or more, it is possible to prevent the hydrolysis reaction of the functional group exhibiting hydrolysis reactivity in the SAM molecule added when preparing the treatment liquid from becoming insufficient. That is, at the stage of generating the treatment liquid, a sufficient amount of SAM molecules to which hydroxyl groups have been introduced can be present in the treatment liquid. As a result, it is possible to suppress the occurrence of film defects and form a SAM with excellent density, even without contacting the treatment liquid with the substrate surface for a long time to form a dense SAM, as in the conventional substrate treatment method. On the other hand, by making the amount of water added 200 ppm or less, it is possible to suppress excessive aggregation of SAM molecules having hydroxyl groups by dehydration condensation reaction. As a result, it is possible to suppress the decrease in density of the SAM molecules to be chemically adsorbed on the substrate surface, and to form a SAM with excellent density.

[0060] The method for preparing the dispersion is not particularly limited, and examples thereof include a method of mixing an organic solvent and water while applying ultrasonic waves, and a method of mixing an organic solvent and water and then applying ultrasonic waves. By applying ultrasonic waves, it is possible to prevent the generation of a mixed liquid in which the organic solvent phase and the water phase are separated. The conditions for applying ultrasonic waves, specifically, for example, the application time, frequency, and sound wave intensity, are not particularly limited as long as the water is dispersed in the organic solvent, and can be set appropriately as needed. In addition, the method for applying ultrasonic waves is also not particularly limited, and examples thereof include a method of immersing an ultrasonic vibrator in the mixed liquid and vibrating the ultrasonic vibrator to apply ultrasonic waves.

[0061] The preparation of the dispersion is preferably carried out in an atmosphere of an inert gas such as nitrogen gas. If the preparation is carried out in an environment in which moisture is present, the moisture in the atmosphere will dissolve in the mixed liquid (or dispersion), and as a result, a dispersion with a predetermined moisture content cannot be obtained, which is not preferable.

[0062] Next, a material capable of forming a SAM (hereinafter referred to as "SAM-forming material") is added to the prepared dispersion to prepare a treatment liquid. When the SAM-forming material is added to the dispersion and after the SAM-forming material is added to the dispersion, it is preferable not to apply ultrasonic waves. By not applying ultrasonic waves, the treatment liquid can be generated so that the SAM molecules exist without agglomerating with each other. By generating the treatment liquid so that the SAM molecules exist without agglomerating with each other, a SAM can be successfully formed in the film formation step S104 described below.

[0063] The SAM-forming material is not particularly limited as long as it has a functional group exhibiting hydrolysis reactivity and contains a molecule capable of forming a SAM. In addition, the SAM-forming material is preferably one having high affinity (solubility) for the above-mentioned organic solvent. Specifically, the SAM-forming material is, for example, octadecyltrichlorosilane (C 18 H 37 SiCl3), decyltrichlorosilane (C 10 H 21The organic silane compounds include trichlorosilyl groups as functional groups exhibiting hydrolysis reactivity.

[0064] Before being added to the treatment liquid, the SAM molecule has a functional group that exhibits hydrolysis reactivity. Therefore, when the SAM-forming material is added to the dispersion liquid, the functional group undergoes a hydrolysis reaction with the water molecules that are uniformly dispersed in the dispersion liquid. As a result, the functional group that exhibits hydrolysis reactivity becomes a hydroxyl group (a functional group that can undergo a dehydration condensation reaction with a hydroxyl group). For example, when the SAM molecule is octadecyltrichlorosilane, the following reaction occurs: C 18 H 37 SiCl3+ 3H2O → C 18 H 37 Si(OH)3+ 3HCl3 As a result, a treatment liquid can be obtained in which SAM molecules with hydroxyl groups (or silanol groups) are present without agglomeration. By preparing a treatment liquid containing SAM molecules with hydroxyl groups in advance, the hydrolysis reaction, which is the rate-limiting step in the SAM film formation process, can be omitted. As a result, it becomes possible to form a SAM film in a shorter time than with conventional treatment liquids.

[0065] The amount of the SAM-forming material added is preferably within a range of 0.05% by mass or more and 5% by mass or less with respect to the total mass of the treatment liquid.

[0066] The treatment liquid may contain known additives as long as they do not impair the effects of the present invention. The additives are not particularly limited, and examples thereof include stabilizers and surfactants.

[0067] The preparation of the treatment liquid is preferably carried out in a stationary state. More specifically, when the SAM-forming material is added to the dispersion, it is not preferable to carry out the preparation while applying mechanical force such as stirring and shaking to the dispersion. When the SAM-forming material is added to the dispersion while applying mechanical force such as stirring and shaking to the dispersion, there is a possibility that the SAM molecules may aggregate with each other. However, by adding the SAM-forming material to the dispersion in a stationary state to prepare the treatment liquid, it is possible to further suppress the aggregation of the SAM molecules with each other and generate the treatment liquid.

[0068] The water content in the treatment liquid is preferably within the range of 50 ppm or more and 200 ppm or less, and more preferably within the range of 50 ppm or more and 150 ppm or less.

[0069] The treatment liquid preparation step S103 can be carried out, for example, under normal temperature and pressure. In this specification, "normal pressure" refers to pressure near the standard atmospheric state (standard atmospheric pressure), and the standard atmospheric state refers to a temperature of about 25°C and an atmospheric pressure of about 101 kPa absolute. "Normal pressure" also includes a pressure that is slightly positive or negative with respect to the standard atmospheric pressure.

[0070] 4. Film formation process The film formation step S104 is a step of bringing a treatment liquid containing a SAM-forming material into contact with the surface of the substrate W to form a SAM.

[0071] The method for contacting the processing liquid with the substrate W is not particularly limited, and examples thereof include a method in which the processing liquid is applied to the surface of the substrate W, a method in which the processing liquid is sprayed onto the surface of the substrate W, and a method in which the substrate W is immersed in the processing liquid.

[0072] An example of a method for applying the processing liquid to the surface of the substrate W is to supply the processing liquid to the center of the surface of the substrate W while rotating the substrate W at a constant speed around its center as an axis. In this way, the processing liquid supplied to the surface of the substrate W flows from near the center of the surface of the substrate W toward the peripheral edge of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and is spread over the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered with the processing liquid, and a liquid film of the processing liquid is formed.

[0073] The conditions for contacting the treatment liquid with the substrate W are not particularly limited. However, the film formation step S104 of this embodiment can shorten the contact time of the treatment liquid compared to the case of forming a SAM film by a conventional method. Specifically, depending on the type of SAM-forming material, its concentration, type of solvent, etc., the time required for the SAM formation step S1 (immersion time 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.

[0074] Next, the process of forming a SAM will be described in more detail using an example in which the SAM-forming material is octadecyltrichlorosilane.

[0075] As shown in Fig. 4(c), when the treatment liquid is supplied to the surface of the substrate W, SAM molecules 5 in which a hydroxyl group has been introduced into octadecyltrichlorosilane are dispersed in the treatment liquid at the beginning of the supply. Fig. 4(c) is an explanatory diagram showing the state in which the treatment liquid is supplied to the surface of the SiO2 layer 1.

[0076] Here, hydroxyl groups have been introduced to the surface of the SiO2 layer 1 by the above-mentioned surface modification step S102. Therefore, as shown in FIG. 5(a), the SAM molecules 5 undergo a dehydration condensation reaction with the hydroxyl groups. More specifically, the hydroxyl groups of the SAM molecules 5 and the hydroxyl groups on the surface of the SiO2 layer 1 undergo a dehydration condensation reaction to form siloxane bonds, and the SAM molecules 5 are chemically adsorbed to the surface of the SiO2 layer 1. The SAM molecules 5 exist in the treatment solution in a state in which they are inhibited from aggregating with each other. Therefore, the dehydration condensation reaction between the hydroxyl groups of the SAM molecules 5 and the hydroxyl groups on the surface of the SiO2 layer 1, which is the rate-determining step in the SAM film formation process, can be promoted. In addition, the SAM molecules 5 can be chemically adsorbed to the surface of the SiO2 layer 1 at a high density. FIG. 5(a) is an explanatory diagram showing how the SAM molecules 5 are chemically adsorbed to the surface of the SiO2 layer 1.

[0077] Next, when the SAM molecules 5 are chemically adsorbed at a high density on the surface of the SiO2 layer 1, an island-like structure of the SAM molecules 5 appears on the surface. Furthermore, in each island, the SAM molecules 5 self-organize and grow (expand) due to hydrophobic and electrostatic interactions with each other, and finally form a SAM6 (see FIG. 5(b)). FIG. 5(b) is an explanatory diagram showing how the SAM molecules 5 self-organize on the surface of the SiO2 layer 1 to form a SAM6.

[0078] 5.Removal process The removal step S105 is a step of removing the treatment liquid remaining on the surface of the SiO2 layer 1 after the film formation step S104. This makes it possible to remove excess SAM molecules 5 that do not contribute to the formation of the SAM 6, more specifically, SAM molecules 5 that are not chemically adsorbed on the surface of the SiO2 layer 1. As a result, it is possible to prevent a film made of unadsorbed SAM molecules 5 from being formed on the SAM 6, and to form a good monolayer.

[0079] The method for removing the processing liquid from the surface of the SiO2 layer 1 is not particularly limited, and examples thereof include a method of applying the removal liquid to the surface of the substrate W, a method of spraying the removal liquid onto the surface of the substrate W, and a method of immersing the substrate W in the removal liquid.

[0080] An example of a method for applying the removing liquid to the surface of the substrate W is to supply the removing liquid to the center of the surface of the substrate W while rotating the substrate W at a constant speed around its center as an axis. In this way, the removing liquid supplied to the surface of the substrate W flows from near the center of the surface of the substrate W toward the peripheral edge of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and is spread over the entire surface of the substrate W. As a result, the processing liquid on the surface of the substrate W is replaced with the removing liquid, and the entire surface of the substrate W is covered with the removing liquid, forming a liquid film of the removing liquid.

[0081] When the SAM-forming material is octadecyltrichlorosilane, the surface of the SiO2 layer 1 in the removal step S105 is as shown in Fig. 5(c). As shown in the figure, SAM molecules 5 that do not contribute to the formation of a SAM 6 are removed from the surface of the SiO2 layer 1 of the substrate W by the removal liquid. Fig. 5(c) is an explanatory diagram showing the state in which excess SAM molecules 5 are removed from the surface of the SiO2 layer 1 in the removal step S105.

[0082] The removal liquid is not particularly limited, but an organic solvent that dissolves the SAM-forming material and has low water solubility is preferred. If the removal liquid can dissolve the SAM-forming material, the excess SAM molecules 5 that do not contribute to the formation of the SAM can be effectively removed from the surface. More specifically, examples of the removal liquid include toluene, decane, and 1,3-bis(trifluoromethyl)benzene. These solvents can be used alone or in combination of two or more.

[0083] 6.Drying process The drying step S106 is intended to remove the removing liquid remaining on the surface of the substrate W. The drying method is not particularly limited, and may be, for example, a method of spraying an inert gas such as nitrogen gas onto the surface of the substrate W. The drying conditions such as the drying time and drying temperature are not particularly limited as long as the removing liquid is removed, and may be set appropriately as necessary.

[0084] As a result, in the SAM formation step S1, as shown in FIG. 5(c), a SAM 6 having excellent denseness and protective performance can be formed on the surface of the SiO2 layer 1. In this embodiment, a surface modification step S102 is performed to introduce hydroxyl groups to the surface of the SiO2 layer 1. This allows the SAM molecules 5 to be chemically adsorbed in areas where the SAM molecules 5 cannot be chemically adsorbed. Furthermore, even in areas where the SAM molecules 5 can be chemically adsorbed, the SAM molecules 5 can be chemically adsorbed on the surface of the SiO2 layer 1 at a high density by further introducing hydroxyl groups. As a result, even if the SAM molecules 5 are not kept in contact with the surface of the SiO2 layer 1 for a long time to form a dense film, the occurrence of film defects can be suppressed, and a SAM 6 having excellent denseness and protective performance can be efficiently formed in a short time.

[0085] In this embodiment, a rinsing step and another drying step may be performed immediately after the drying step S106. By performing the rinsing step, the removing liquid can be removed from the surface of the SiO2 layer 1. Also, by performing another drying step, the rinsing liquid used in the rinsing step can be removed.

[0086] The rinse liquid in the rinse step is not particularly limited, and may be, for example, DIW, etc. The method of supplying the rinse liquid to the surface of the substrate W is not particularly limited, and may be, for example, a method of applying the rinse liquid to the surface of the substrate W, a method of spraying the rinse liquid onto the surface of the substrate W, a method of immersing the substrate W in the rinse liquid, etc.

[0087] An example of a method for applying the rinse liquid to the surface of the substrate W is to supply the rinse liquid to the central portion of the surface of the substrate W while rotating the substrate W at a constant speed around its central portion as an axis. In this way, the rinse liquid supplied to the surface of the substrate W flows from near the center of the surface of the substrate W toward the peripheral portion of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and is spread over the entire surface of the substrate W. As a result, the removing liquid on the surface of the substrate W is replaced with the rinse liquid, and the entire surface of the substrate W is covered with the rinse liquid, forming a liquid film of the rinse liquid.

[0088] The other drying step is intended to remove the rinsing liquid remaining on the surface of the substrate W. The drying method is not particularly limited, and examples thereof include a method of spraying an inert gas such as nitrogen gas onto the surface of the substrate W. The drying conditions such as the drying time and drying temperature are not particularly limited as long as the rinsing liquid is removed, and can be set appropriately as necessary.

[0089] <Etching process (single wafer type)> The etching step S2 is a step of selectively etching the SiN layer 2, which is a sacrificial layer and a layer to be etched. More specifically, this is a step of bringing an etching solution into contact with the SiN layer 2 through the memory trench 4 and removing the SiN layer 2. In this step, the SAM 6 functions as a protective layer to protect the SiO2 layer 1. This makes it possible to effectively prevent the SiO2 layer 1 from being etched.

[0090] As a method for applying the etching liquid to the surface of the substrate W, for example, in the case of a single-wafer process, the etching 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 center as an axis. In this way, the etching liquid supplied to the surface of the substrate W flows from near the center of the surface of the substrate W toward the peripheral edge of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and is diffused over the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered with the etching liquid, and a liquid film of the etching liquid is formed.

[0091] The etching liquid can be appropriately set in consideration of the constituent material of the layer to be etched, the etching rate, etc. When the layer to be etched is a SiN layer 2 as in this embodiment, for example, an aqueous solution of phosphoric acid (H3PO4) or hydrofluoric acid (for example, HF:DIW=1:100 in volume ratio) can be used as the etching liquid. The concentration of the etching liquid can also be appropriately set in consideration of the constituent material of the layer to be etched, the etching rate, etc.

[0092] Furthermore, the etching temperature (that is, the temperature of the etching solution) and the etch rate for the layer to be etched can be appropriately set in consideration of the constituent material of the layer to be etched.

[0093] It is preferable to sequentially perform a rinsing step for removing the etching liquid and a drying step immediately after the etching step S2. The rinsing method in the rinsing step is not particularly limited, and examples thereof include a method of supplying a rinsing liquid to the surface of the substrate W and a method of immersing the substrate W in the rinsing liquid. The rinsing liquid is not particularly limited, and examples thereof include DIW. In addition, cleaning conditions such as the rinsing time and the temperature of the rinsing liquid are not particularly limited, and can be set appropriately as needed. The drying step is intended to remove the rinsing liquid remaining on the surface of the substrate W. The drying method is not particularly limited, and examples thereof include a method of spraying an inert gas such as nitrogen gas onto the surface of the substrate W. Drying conditions such as the drying time and the drying temperature are not particularly limited, and can be set appropriately as needed.

[0094] As a result, in the etching step S2, only the SiN layer 2 can be selectively removed as shown in FIG. 2(c). In addition, the SAM6, which has excellent density and protective performance, covers and protects the surface of the SiO2 layer 1, so that the SiO2 layer 1 can be prevented from being etched and the etched silicon components can be prevented from precipitating and adhering to the surface of the SiO2 layer 1. Furthermore, the tolerance range of the silicon concentration contained in the etching solution such as phosphoric acid can be increased. FIG. 2(c) is a partial enlarged view of the portion surrounded by B in the laminate in FIG. 1(b), showing the state in which the SiN layer 2 has been etched.

[0095] [Substrate processing equipment (semiconductor manufacturing equipment)] Next, the substrate processing apparatus according to this embodiment will be described below by taking as an example a case where it is applied to a semiconductor manufacturing apparatus.

[0096] The semiconductor manufacturing apparatus 100 of this embodiment is a single-wafer processing unit used to form a SAM and etch a layer to be etched, and includes, as shown in Fig. 6, a substrate holding unit 110 for holding a substrate W, a pretreatment liquid supply unit 120 for supplying a pretreatment liquid to the surface Wf of the substrate W, a surface modification liquid supply unit (surface modification unit) 130 for supplying a surface modification liquid to the surface Wf of the substrate W, a processing liquid supply unit 140 for supplying a processing liquid to the surface Wf of the substrate W, an ultrasonic wave application unit, a removing liquid supply unit 150 for supplying a removing liquid, an inert gas supply unit (not shown) for supplying an inert gas, an etching liquid supply unit 160, a chamber 170 which is a container for accommodating the substrate W, a splash prevention cup 180 for collecting the processing liquid, a swivel drive unit 190 for independently swivel-driving the arms of each unit described later, and a control unit 300. The semiconductor manufacturing apparatus 100 may also include a loading / unloading unit (not shown) for loading or unloading the substrate W. 6 is an explanatory diagram showing a schematic configuration of a semiconductor manufacturing apparatus 100 according to this embodiment. In this figure, XYZ orthogonal coordinate axes are appropriately displayed to clarify the directional relationship of the illustrated objects. Here, the XY plane represents the horizontal plane, and the +Z direction represents the vertical upward direction.

[0097] <Substrate holding part> The substrate holding unit 110 is a means for holding the substrate W, and as shown in Fig. 6, holds and rotates the substrate W in a substantially horizontal position with the surface Wf of the substrate W facing upward. The substrate holding unit 110 has a spin chuck 113 in which a spin base 111 and a rotation support shaft 112 are integrally connected. The spin base 111 has a substantially circular shape in a plan view, and a hollow rotation support shaft 112 extending substantially vertically is fixed to the center of the spin base 111. The rotation support shaft 112 is connected to a rotation shaft of a chuck rotation mechanism 114 including a motor. The chuck rotation mechanism 114 is housed in a cylindrical casing 115, and the rotation support shaft 112 is supported by the casing 115 so as to be rotatable about a vertical rotation axis J1.

[0098] The chuck rotation mechanism 114 can rotate the rotation support shaft 112 around the rotation axis J1 by being driven by a chuck drive unit (not shown) of the control unit 300. This causes the spin base 111 attached to the upper end of the rotation support shaft 112 to rotate around the rotation axis J1 at a constant speed. The control unit 300 can adjust the rotation speed of the spin base 111 by controlling the chuck rotation mechanism 114 via the chuck drive unit.

[0099] A plurality of chuck pins 116 for gripping the peripheral edge of the substrate W are provided upright near the peripheral edge of the spin base 111. The number of chuck pins 116 to be provided is not particularly limited, but it is preferable to provide at least three or more in order to reliably hold the circular substrate W. In this embodiment, three chuck pins 116 are arranged at equal intervals along the peripheral edge of the spin base 111. Each chuck pin 116 includes a substrate support pin that supports the peripheral edge of the substrate W from below, and a substrate holding pin that holds the substrate W by pressing against the outer circumferential end face of the substrate W supported by the substrate support pin.

[0100] <Pre-treatment liquid supply unit> The pre-treatment liquid supply unit 120 according to this embodiment is a unit that supplies a pre-treatment liquid to the front surface Wf of the substrate W. As shown in FIG. 6 , the pre-treatment liquid supply unit 120 includes a pre-treatment liquid storage unit 121, a nozzle 122, and an arm 123.

[0101] 7, the pretreatment liquid storage unit 121 includes a pressurizing unit 124 and a pretreatment liquid tank 125. Note that, Fig. 7 is an explanatory diagram showing a schematic configuration of the pretreatment liquid storage unit 121 in the pretreatment liquid supply unit 120.

[0102] The pressurizing unit 124 includes a nitrogen gas supply source 124a which is a gas supply source for pressurizing the inside of the pretreatment liquid tank 125, a pump (not shown) for pressurizing the nitrogen gas, a nitrogen gas supply pipe 124b, and a valve 124c provided midway along the nitrogen gas supply pipe 124b.

[0103] The nitrogen gas supply pipe 124b is connected to the treatment liquid tank 125. In addition, the valve 124c is electrically connected to the control unit 300, and the opening and closing of the valve 124c can be controlled by an operation command from the control unit 300. When the valve 124c is opened by an operation command from the control unit 300, nitrogen gas can be supplied to the treatment liquid tank 125.

[0104] The pretreatment liquid tank 125 may include an agitation unit that agitates the pretreatment liquid in the pretreatment liquid tank 125, and a temperature adjustment unit that adjusts the temperature of the pretreatment liquid (neither is shown). The agitation unit may include a rotation unit that agitates the pretreatment liquid, and an agitation control unit that controls the rotation of the rotation unit. The agitation control unit is electrically connected to the control unit 300, and the rotation unit includes, for example, a propeller-shaped agitation blade at the lower end of the rotation shaft. The control unit 300 issues an operation command to the agitation control unit to rotate the rotation unit, thereby allowing the agitation blade to agitate the pretreatment liquid. As a result, the concentration and temperature of the pretreatment liquid in the pretreatment liquid tank 125 can be made uniform.

[0105] Furthermore, a discharge pipe 125a for supplying the pre-treatment liquid to the nozzle 122 is connected to the pre-treatment liquid tank 125. A discharge valve 125b is provided midway along the discharge pipe 125a. The discharge valve 125b is also electrically connected to the control unit 300. This allows the opening and closing of these valves to be controlled by an operation command from the control unit 300. When the discharge valve 125b is opened by an operation command from the control unit 300, the pre-treatment liquid is pressure-fed to the nozzle 122 via the discharge pipe 125a.

[0106] The nozzle 122 is attached to the tip of an arm 123 that extends horizontally, and is disposed above the spin base 111 when discharging the pre-treatment liquid. The arm 123 is connected to a rotation drive unit 190 via a rotation shaft (not shown). The rotation drive unit 190 is electrically connected to a control unit 300, and rotates the arm 123 in response to an operation command from the control unit 300. As the arm 123 rotates, the nozzle 122 also moves.

[0107] <Surface modification liquid supply unit (surface modification unit)> The surface modification liquid supply unit 130 according to this embodiment is a means for supplying a surface modification liquid to the front surface Wf of the substrate W. As shown in FIG. 6, the surface modification liquid supply unit 130 includes a surface modification liquid storage unit 131, a nozzle 132, and an arm 133.

[0108] 8, the surface modification liquid storage unit 131 has a function of supplying the surface modification liquid to the nozzle 132, and includes a pressurizing unit 134 and a surface modification liquid tank 135. Fig. 8 is an explanatory diagram showing a schematic configuration of the surface modification liquid storage unit 131 in the surface modification liquid supply unit 130.

[0109] The pressurizing unit 134 includes a nitrogen gas supply source 134a which is a gas supply source for pressurizing the inside of the surface modification liquid tank 135, a pump (not shown) for pressurizing the nitrogen gas, a nitrogen gas supply pipe 134b, and a valve 134c provided midway along the nitrogen gas supply pipe 134b.

[0110] The nitrogen gas supply pipe 134b is connected to the surface modification liquid tank 135. In addition, the valve 134c is electrically connected to the control unit 300, and the opening and closing of the valve 134c can be controlled by an operation command from the control unit 300. When the valve 134c is opened by an operation command from the control unit 300, nitrogen gas can be supplied to the surface modification liquid tank 135.

[0111] The surface-modifying liquid tank 135 may include an agitation unit that agitates the surface-modifying liquid in the surface-modifying liquid tank 135, and a temperature adjustment unit that adjusts the temperature of the surface-modifying liquid (neither is shown). The agitation unit may include a rotation unit that agitates the surface-modifying liquid in the surface-modifying liquid tank 135, and an agitation control unit that controls the rotation of the rotation unit. The agitation control unit is electrically connected to the control unit 300, and the rotation unit is provided with, for example, a propeller-shaped agitation blade at the lower end of the rotation shaft. The control unit 300 issues an operation command to the agitation control unit to rotate the rotation unit, thereby allowing the agitation blade to agitate the surface-modifying liquid. As a result, the concentration and temperature of the surface-modifying liquid in the surface-modifying liquid tank 135 can be made uniform.

[0112] Furthermore, a discharge pipe 135a for supplying the surface modification liquid to the nozzle 132 is connected to the surface modification liquid tank 135. A discharge valve 135b is provided midway along the discharge pipe 135a. The discharge valve 135b is electrically connected to the control unit 300. This allows the opening and closing of the discharge valve 135b to be controlled by an operation command from the control unit 300. When the discharge valve 135b is opened by an operation command from the control unit 300, the surface modification liquid is pressure-fed to the nozzle 132 via the discharge pipe 135a.

[0113] The nozzle 132 is attached to the tip of an arm 133 that extends horizontally, and is disposed above the spin base 111 when discharging the surface modification liquid. The arm 133 is connected to a rotation drive unit 190 via a rotation shaft (not shown). The rotation drive unit 190 is electrically connected to a control unit 300, and rotates the arm 133 according to an operation command from the control unit 300. As the arm 133 rotates, the nozzle 132 also moves.

[0114] <Processing liquid supply unit> The processing liquid supply unit 140 according to this embodiment is a unit for supplying a processing liquid to the front surface Wf of the substrate W. As shown in FIG. 6, the processing liquid supply unit 140 includes a processing liquid storage unit 141, a nozzle 142, and an arm 143.

[0115] 9, the treatment liquid storage section 141 includes an organic solvent supply section 144, a water supply section 145, a SAM-forming material supply section 146, a treatment liquid tank 147, a temperature adjustment section 148, and an inert gas supply section 149. Note that, Fig. 9 is an explanatory diagram showing a schematic configuration of the treatment liquid storage section 141 and the ultrasonic wave application section 191 in the treatment liquid supply section 140.

[0116] The organic solvent supply unit 144 includes an organic solvent storage unit 144a for storing an organic solvent, an organic solvent supply pipe 144b for supplying the organic solvent to the treatment liquid tank 147, and a valve 144c provided in the middle of the organic solvent supply pipe 144b. The valve 144c is electrically connected to the control unit 300. This allows the valve 144c to be opened and closed by an operation command from the control unit 300. When 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 through the organic solvent supply pipe 144b. The organic solvent in the organic solvent storage unit 144a is pressurized by a pressurizing means (not shown) and sent to the organic solvent supply pipe 144b. The pressurizing means is not particularly limited, and a known means such as a pump can be used.

[0117] 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 provided midway along the path of the water supply pipe 145b. The valve 145c is electrically connected to the control unit 300. This allows the valve 145c to be opened and closed by an operation command from the control unit 300. When the valve 145c is opened by an operation command from the control unit 300, water is supplied to the treatment liquid tank 147 via the water supply pipe 145b. The water in the water storage unit 145a is pressurized by a pressurizing means (not shown) and sent to the water supply pipe 145b. The pressurizing means is not particularly limited, and a known means such as a pump can be used.

[0118] The SAM-forming material supply unit 146 includes a SAM-forming material storage unit 146a for storing the SAM-forming material, a SAM-forming material supply pipe 146b for supplying the SAM-forming material to the treatment liquid tank 147, and a valve 146c provided in the middle of the SAM-forming material supply pipe 146b. The valve 146c is electrically connected to the control unit 300. This allows the valve 146c to be opened and closed by an operation command from the control unit 300. When the valve 146c is opened by an operation command from the control unit 300, the SAM-forming material is supplied to the treatment liquid tank 147 through the SAM-forming material supply pipe 146b. The SAM-forming material in the SAM-forming material storage unit 146a is pressurized by a pressurizing means (not shown) and sent to the SAM-forming material supply pipe 146b. The pressurizing means is not particularly limited, and a known means such as a pump can be used.

[0119] The treatment liquid tank 147 mixes the organic solvent supplied from the organic solvent supply unit 144 with the water supplied from the water supply unit 145, and the ultrasonic application unit 191 applies ultrasonic waves to the resulting mixture to generate a dispersion in which water is uniformly dispersed in the organic solvent. Alternatively, the ultrasonic application unit 191 can apply ultrasonic waves while mixing the organic solvent supplied from the organic solvent supply unit 144 with the water supplied from the water supply unit 145 to generate the dispersion. Furthermore, a treatment liquid can be generated by supplying a SAM-forming material from the SAM-forming material supply unit 146 while storing the generated dispersion.

[0120] The processing liquid tank 147 may include a temperature adjustment unit 148 for adjusting the temperature of the dispersion liquid and processing liquid stored therein. 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 making it possible to control the liquid temperature of the dispersion liquid when the dispersion liquid is generated. This makes it possible to prevent water in the dispersion liquid from evaporating (evaporating) and causing a change in the composition of the dispersion liquid.

[0121] The inert gas supply unit 149 includes an inert gas supply source 149a which is a supply source for supplying an inert gas into the processing liquid tank 147, a pump (not shown) for pressurizing the inert gas, an inert gas supply pipe 149b, and a valve 149c provided midway along the inert gas supply pipe 149b.

[0122] The inert gas supply pipe 149b is connected to the treatment liquid tank 147. The valve 149c is electrically connected to the control unit 300, and the opening and closing of the valve 149c can be controlled by an operation command from the control unit 300. When the valve is opened by an operation command from the control unit 300, the inert gas can be supplied to the treatment liquid tank 147. This allows the generation of the dispersion liquid and the treatment liquid to be performed under an atmosphere of the inert gas. The inert gas is not particularly limited, and examples thereof include nitrogen gas.

[0123] Further, a discharge pipe 147a for supplying the processing liquid to the nozzle 142 is connected to the processing liquid tank 147. A discharge valve 147b is provided in the middle of the discharge pipe 147a. The discharge valve 147b is also electrically connected to the control unit 300. This allows the opening and closing of the discharge valve 147b to be controlled by an operation command from the control unit 300. When the discharge valve 147b and the valve 149c are opened and the valves 144c, 145c, and 146c are closed by an operation command from the control unit 300, the processing liquid is pressure-fed to the nozzle 142 via the discharge pipe 147a.

[0124] The nozzle 142 is attached to the tip of an arm 143 that extends horizontally, and is disposed above the spin base 111 when discharging the processing liquid. The arm 143 is connected to a rotation drive unit 190 via a rotation shaft (not shown). The rotation drive unit 190 is electrically connected to a control unit 300, and rotates the arm 143 in response to an operation command from the control unit 300. As the arm 143 rotates, the nozzle 142 also moves.

[0125] <Ultrasonic application unit> 9, the ultrasonic wave application unit 191 is a means for applying ultrasonic waves when generating a dispersion liquid in the processing liquid tank 147 of the processing liquid supply unit 140. The ultrasonic wave application unit 191 is electrically connected to the control unit 300, and the application of ultrasonic waves can be controlled by an operation command from the control unit 300.

[0126] The ultrasonic wave application unit 191 includes, for example, an ultrasonic vibrator provided in the treatment liquid tank 147, and an oscillator that applies a drive voltage to the ultrasonic vibrator (neither is shown). An example of the ultrasonic vibrator includes a piezoelectric body such as piezoelectric ceramics and a pair of electrodes provided on the piezoelectric body. The pair of electrodes are in contact with the piezoelectric body and are also electrically connected to the oscillator. When the oscillator outputs, for example, a high-frequency voltage as a drive voltage to the ultrasonic vibrator in response to an operation command from the control unit 300, the drive voltage is applied between the pair of electrodes, and the drive voltage is applied to the piezoelectric body. The piezoelectric body to which the drive voltage is applied vibrates by alternately repeating contraction and expansion in response to the drive voltage from the oscillator. This allows ultrasonic waves to be applied to the mixture of water and organic solvent stored in the treatment liquid tank 147.

[0127] <Removal liquid supply section> The removing liquid supply unit 150 according to this embodiment is a unit that supplies a removing liquid to the front 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 an arm 153.

[0128] 10, the removing liquid storage unit 151 has a function of supplying the removing liquid to the nozzle 152, and includes a pressurizing unit 154 and a removing liquid tank 155. Fig. 10 is an explanatory diagram showing a schematic configuration of the removing liquid storage unit 151 in the removing liquid supply unit 150.

[0129] The pressurizing unit 154 includes a nitrogen gas supply source 154a which is a gas supply source for pressurizing the inside of the removal liquid tank 155, a pump (not shown) for pressurizing the nitrogen gas, a nitrogen gas supply pipe 154b, and a valve 154c provided midway along the nitrogen gas supply pipe 154b.

[0130] The nitrogen gas supply pipe 154b is connected to the removal liquid tank 155. In addition, the valve 154c is electrically connected to the control unit 300, and the opening and closing of the valve 154c can be controlled by an operation command from the control unit 300. When the valve 154c is opened by an operation command from the control unit 300, nitrogen gas can be supplied to the removal liquid tank 155.

[0131] The removal liquid tank 155 may include an agitation unit that agitates the removal liquid in the removal liquid tank 155, and a temperature adjustment unit that adjusts the temperature of the removal liquid (neither is shown). The agitation unit may include a rotation unit that agitates the removal liquid in the removal liquid tank 155, and an agitation control unit that controls the rotation of the rotation unit. The agitation control unit is electrically connected to the control unit 300, and the rotation unit is provided with, for example, a propeller-shaped agitation blade at the lower end of the rotation shaft. The control unit 300 issues an operation command to the agitation control unit to rotate the rotation unit, thereby agitating the removal liquid with the agitation blade. As a result, the concentration and temperature of the removal liquid can be made uniform in the removal liquid tank 155.

[0132] Furthermore, a discharge pipe 155a for supplying the removal liquid to the nozzle 152 is connected to the removal liquid tank 155. A discharge valve 155b is provided midway along the discharge pipe 155a. The discharge valve 155b is electrically connected to the control unit 300. This allows the opening and closing of the discharge valve 155b to be controlled by an operation command from the control unit 300. When the discharge valve 155b is opened by an operation command from the control unit 300, the removal liquid is pressure-fed to the nozzle 152 via the discharge pipe 155a.

[0133] The nozzle 152 is attached to the tip of an arm 153 that extends horizontally, and is positioned above the spin base 111 when discharging the removal liquid. The arm 153 is connected to a rotation drive unit 190 via a rotation shaft (not shown). The rotation drive unit 190 is electrically connected to a control unit 300, and rotates the arm 153 in response to an operation command from the control unit 300. As the arm 153 rotates, the nozzle 152 also moves.

[0134] <Inert gas supply section> The inert gas supply unit is a means for supplying an inert gas to the front surface Wf of the substrate W. The inert gas supply unit has an inert gas reservoir, a nozzle, and an arm (none of which are shown).

[0135] The inert gas storage unit has a function of supplying an inert gas to the nozzle, and includes an inert gas tank for storing the inert gas, an inert gas temperature adjustment unit for adjusting the temperature of the inert gas stored in the inert gas tank, and a pipe. The inert gas stored in the inert gas tank can be, for example, nitrogen gas.

[0136] The inert gas temperature adjustment unit is electrically connected to the control unit 300, and adjusts the temperature by heating or cooling the inert gas stored in the inert gas tank according to an operation command from the control unit 300. The inert gas temperature adjustment unit is not particularly limited, and any known temperature adjustment mechanism such as a Peltier element or a pipe through which temperature-adjusted water flows can be used.

[0137] The inert gas storage section is connected to the nozzle through a pipe, and a valve is inserted in the middle of the pipe. The inert gas in the inert gas tank is pressurized by a pressurizing means (not shown) and sent to the pipe. The pressurizing means can be realized by compressing and storing the inert gas in the inert gas tank, in addition to pressurization by a pump or the like.

[0138] The valve is electrically connected to the control unit 300 and is normally closed. Opening and closing of the valve is controlled by an operation command from the control unit 300. When the valve is opened by an operation command from the control unit 300, an inert gas is supplied from a nozzle through a pipe to the front surface Wf of the substrate W.

[0139] The nozzle is attached to the tip of a horizontally extending arm, and is positioned above the spin base 111 when discharging the inert gas. The arm is connected to a rotation drive unit 190 via a rotation shaft (not shown). The rotation drive unit 190 is electrically connected to the control unit 300, and rotates the arm according to an operation command from the control unit 300. The nozzle also moves as the arm rotates.

[0140] <Etching solution supply unit> The etching liquid supply unit 160 is a means for supplying an etching liquid to the front surface Wf of the substrate W. The etching liquid supply unit 160 has an etching liquid storage unit 161, a nozzle 162, and an arm 163, as shown in FIG.

[0141] 11, the etching liquid storage unit 161 includes at least an etching liquid tank 164, a temperature regulator 165, a liquid delivery pump 166, and a particle filter 167. Note that, FIG. 11 is an explanatory diagram showing a schematic configuration of the etching liquid storage unit 161 in the etching liquid supply unit 160.

[0142] The etching solution tank 164 may include an agitation unit (not shown) that agitates the etching solution in the etching solution tank 164. The agitation unit may include a rotation unit that agitates the etching solution and an agitation control unit that controls the rotation of the rotation unit. The agitation control unit is electrically connected to the control unit 300, and the rotation unit includes, for example, a propeller-shaped agitation blade at the lower end of the rotation shaft. The control unit 300 issues an operation command to the agitation control unit to rotate the rotation unit, thereby agitating the etching solution with the agitation blade. As a result, the concentration and temperature of the etching solution in the etching solution tank 164 can be made uniform.

[0143] The etching solution tank 164 is provided with a mixer 168 capable of mixing an etching solution with a chemical and DIW from an external supply source (not shown) to prepare an etching solution of a predetermined concentration. The chemical is a solute that functions as an etchant. Examples of the chemical include the aforementioned phosphoric acid and hydrogen fluoride.

[0144] Further, the etching solution tank 164 is connected to a discharge pipe 169 for supplying the etching solution to the nozzle 162. A temperature regulator 165, a liquid delivery pump 166, and a particle filter 167 are sequentially interposed in the middle of the discharge pipe 169 from upstream to downstream. The temperature regulator 165 and the liquid delivery pump 166 are electrically connected to the control unit 300. This allows the temperature of the etching solution to be supplied to the nozzle 162 to be controlled by an operation command from the control unit 300. Furthermore, when the liquid delivery pump 166 is controlled by an operation command from the control unit 300, the etching solution can be pressure-fed to the nozzle 162 through the discharge pipe 169. The particle filter 167 can remove foreign matter such as particles in the etching solution.

[0145] The nozzle 162 is attached to the tip of an arm 163 that extends horizontally, and is positioned above the spin base 111 when discharging the etching liquid. The arm 163 is connected to a rotation drive unit 190 via a rotation shaft (not shown). The rotation drive unit 190 is electrically connected to a control unit 300, and rotates the arm 163 according to an operation command from the control unit 300. As the arm 163 rotates, the nozzle 162 also moves.

[0146] <Shatterproof cup> The splash prevention cup 180 is provided so as to surround the spin base 111. The splash prevention cup 180 is connected to a lift drive mechanism (not shown) and can be raised and lowered in the vertical direction. When supplying a processing liquid or the like to the front surface Wf of the substrate W, the splash prevention cup 180 is positioned at a predetermined position by the lift drive mechanism and surrounds the substrate W held by the chuck pins 116 from a lateral position. This makes it possible to collect the processing liquid or the like splashed from the substrate W or the spin base 111.

[0147] <Control Unit> The control unit 300 is electrically connected to each part of the semiconductor manufacturing apparatus and controls the operation of each part. The control unit 300 is composed of a computer having an arithmetic unit and a storage unit. As the arithmetic unit, a CPU that performs various arithmetic processes is used. The storage unit includes a read-only memory (ROM) that stores a substrate processing program and an etching processing program, a random access memory (RAM) that stores various information and is readable and writable, and a magnetic disk that stores control software, data, etc. The magnetic disk stores in advance processing conditions including the generation (mixing) conditions of the dispersion liquid and the processing liquid; the supply conditions of the pretreatment liquid, the surface modification liquid, the processing liquid, the removal liquid, the inert gas, and the etching liquid; the application conditions of ultrasonic waves; the rinsing conditions; the drying conditions; the film formation conditions of SAM; and the etching conditions, etc. The CPU reads the processing conditions into the RAM and controls each part of the semiconductor manufacturing apparatus according to the content thereof.

[0148] (Second Embodiment) The second embodiment of the present invention will be described below. This embodiment is different from the first embodiment in that the surface modification step is performed by a dry method using ultraviolet irradiation. Also, the etching step is different in that it is performed in a batch type instead of a single-wafer type. Even with such a configuration, a SAM with a high film density, excellent denseness, and good suppression or reduction of film defects can be efficiently formed on the substrate surface in a shorter time than the conventional film formation method, and has excellent protection performance.

[0149] [Substrate Processing Method (Manufacturing Method of Semiconductor Device)] The substrate processing method (manufacturing method of semiconductor device) according to this embodiment will be described below. FIG. 12 is a flowchart showing an example of the overall flow of the substrate processing method according to the second embodiment of the present invention.

[0150] [SAM Formation Step] In the SAM formation step S1' shown in FIG. 12, the pretreatment step S101, the processing liquid preparation step S103, the film formation step S104, the removal step S105, and the drying step S106 are the same as those in the first embodiment. Therefore, the detailed description of these steps is omitted.

[0151] 1. Surface modification process (dry method) The surface modification step S102' is a step of modifying the surface of the SiO2 layer 1 so that the area where chemisorption of SAM molecules is difficult is changed to an area where chemisorption of SAM molecules is possible, similar to the surface modification step S102 in the first embodiment. Also, the surface modification step is a step of modifying the surface so that the area where chemisorption of SAM molecules is possible at a high density is changed.

[0152] In this embodiment, the surface of the SiO2 layer 1 is modified by a dry method using ultraviolet irradiation. In the case of ultraviolet irradiation, the ultraviolet irradiation conditions such as the wavelength of the light source, irradiation intensity, and irradiation time are not particularly limited as long as hydroxyl groups can be introduced to the surface of the SiO2 layer 1 to an extent that the SAM molecules 5 can be chemically adsorbed. In addition, the ultraviolet irradiation is performed in an atmosphere containing oxygen atoms, such as air.

[0153] <Etching process (batch type)> The etching step S2' is a step of selectively etching the SiN layer 2, which is the layer to be etched, by immersing the substrate W after the SAM formation in an etching solution.

[0154] The method of immersing the substrate W in the etching solution is, for example, performed with the substrate W in an upright position. Here, the "upright position" refers to a position in which the surface of the substrate W is aligned in a direction substantially perpendicular to a horizontal plane, and includes a vertical position. The etching solution may be the same as that described in the first embodiment. In addition, the etching temperature (i.e., the liquid temperature of the etching solution) and the etch rate for the layer to be etched may be appropriately set in consideration of the constituent material of the layer to be etched, as in the first embodiment.

[0155] [Substrate processing equipment (semiconductor manufacturing equipment)] Next, the substrate processing apparatus according to this embodiment will be described below by taking as an example a case where it is applied to a semiconductor manufacturing apparatus.

[0156] The semiconductor manufacturing apparatus of this embodiment differs from the substrate processing apparatus of the first embodiment in that it is equipped with at least a single-wafer substrate processing unit for forming a SAM and a batch-type etching processing unit for etching the layer to be etched.

[0157] <Substrate processing unit> As shown in FIG. 13, the substrate processing unit 200 of this embodiment is different from the semiconductor manufacturing apparatus 100 of the first embodiment in that an ultraviolet ray irradiation unit 210 is provided as a surface modification unit instead of a surface modification liquid supply unit. FIG. 13 is an explanatory diagram showing a schematic configuration of the substrate processing unit according to this embodiment. In this figure, some of the configuration common to the semiconductor manufacturing apparatus 100 of the first embodiment is omitted. In this figure, XYZ orthogonal coordinate axes are appropriately displayed to clarify the directional relationship of the illustrated objects. Here, the XY plane represents the horizontal plane, and the +Z direction represents the vertical upward direction.

[0158] The ultraviolet ray irradiation unit 210 is disposed above the substrate holding unit 110 (in the direction indicated by the arrow Z in FIG. 13 ) so as to be able to irradiate ultraviolet rays onto the front surface Wf of the substrate W held by the substrate holding unit 110 inside the chamber 170. The ultraviolet ray irradiation unit 210 includes at least a plurality of light source units 211 and quartz glass 212.

[0159] The light source section 211 shown in FIG. 13 is a line light source, and is arranged so that its longitudinal direction is parallel to the direction indicated by Y in FIG. 13. The light source sections 211 are also arranged in the direction indicated by the arrow X so as to be equally spaced from one another. However, the light source section 211 of the present invention is not limited to this embodiment. For example, the light source section 211 may be ring-shaped light source sections having different diameters arranged concentrically. The light source section may also be a point light source. In this case, it is preferable that the multiple light source sections are arranged so as to be equally spaced from one another in a plane.

[0160] The type of the light source unit 211 is not particularly limited, and for example, a low pressure mercury lamp, a high pressure mercury lamp, a potassium lamp, a mercury xenon lamp, a flash lamp, an excimer lamp, a metal halide lamp, and a UV (ultraviolet)-LED (Light Emitting Diode) can be used. The multiple light source units 211 may be of the same type or different types. When multiple light source units of different types are used as the light source unit 211, they can be arranged with different peak wavelengths, light intensities, etc.

[0161] The quartz glass 212 is disposed between the light source unit 211 and the substrate W. The quartz glass 212 is a plate-like body, and is provided so as to be parallel to the horizontal direction. The quartz glass 212 has optical transparency, heat resistance, and corrosion resistance to ultraviolet rays, and allows the ultraviolet rays irradiated from the light source unit 211 to pass through, enabling the ultraviolet rays to be irradiated onto the surface Wf of the substrate W. Furthermore, the quartz glass 212 can protect the light source unit 211 from the atmosphere in the chamber 170.

[0162] <Etching processing unit> The etching processing unit of this embodiment is a batch-type processing unit used for etching a layer to be etched, and performs an etching step S2' on a substrate W on which a SAM has been formed in the substrate processing unit. As shown in Figs. 14 and 15, the etching processing unit at least includes a substrate transport unit (not shown), a lifter 220, and a processing tank 230 for storing an etching solution. Fig. 14 is a side view showing a schematic configuration of the lifter 220 in the semiconductor manufacturing apparatus of this embodiment. Also, Fig. 15 is a cross-sectional view showing a state in which a plurality of substrates W on which a SAM has been formed in this embodiment are immersed in an etching solution.

[0163] The substrate transport unit transports the substrate W on which the SAM has been formed in the substrate processing unit to the etching processing unit. The substrate transport unit includes, for example, an articulated robot capable of transporting the substrate W. The tip of the articulated robot includes a transport arm capable of loading the substrates W all at once in a horizontal position.

[0164] As shown in FIG. 14, the lifter 220 includes a flat back plate 221, a plurality (three) of holding bars 222, and a lifting mechanism (not shown). The back plate 221 stands upright, and at its lower end, the holding bars 222 extend in one direction so as to be perpendicular to the back plate 221. The holding bars 222 are provided with a plurality of grooves 223 arranged in the extending direction. The plurality of grooves 223 are arranged at equal intervals and spaced apart from one another. Furthermore, each groove 223 extends in a direction perpendicular to the extending direction of the holding bar 222, and a plurality of substrates W can be fitted in the holding bars 222 in an upright position. As a result, the holding bars 222 can abut against and support the group of substrates W from below in an upright position, and hold them collectively. The number of holding bars 222 is not particularly limited as long as it is plural. Furthermore, the number of grooves 223 provided in the holding rod 222 is not particularly limited and may be set appropriately depending on the number of substrates W to be held. Furthermore, the lifting mechanism can raise or lower the lifter 220 in the Z direction shown in Fig. 15. This allows the lifter 220, which is collectively holding the group of substrates W, to be moved into or removed from the processing tank 230.

[0165] 15, the processing tank 230 includes an injection pipe 231 for supplying an etching solution into the processing tank 230, an inner tank 232 for storing the etching solution, and an outer tank 233 provided on the periphery of the upper opening of the inner tank 232. The injection pipe 231 is provided on the bottom of the inner tank 232, and enables the etching solution to be supplied in an upflow manner to the inner tank 232. The outer tank 233 enables the etching solution overflowing from the inner tank 232 to be collected. The injection pipe 231 may be connected to the etching solution storage section 161 described in the first embodiment, for example, via a discharge pipe 169.

[0166] (Other matters) In the above description, the most preferred embodiment of the present invention has been described. However, the present invention is not limited to this embodiment. For example, in the first embodiment, the etching process of the SiN2 layer is performed in a single-wafer manner, but the etching process may be performed in a batch manner as described in the second embodiment. In the first embodiment, the surface modification process is performed in a wet manner, but the surface modification process may be performed in a dry manner using ultraviolet light irradiation as described in the second embodiment. Even in these embodiments, a SAM having high film density and excellent compactness, in which the occurrence of film defects is well suppressed or reduced, and excellent protective performance can be efficiently formed on the substrate surface in a shorter time than in the conventional film formation method. EXAMPLES

[0167] Preferred examples of the present invention are described in detail below. However, the materials, amounts, conditions, etc. described in the examples are not intended to limit the scope of the present invention unless otherwise specified.

[0168] Example 1 A substrate with a SiO2 film (thickness 100 nm) formed on its surface was prepared and immersed in a hydrogen fluoride aqueous solution (pretreatment liquid) for 1 minute (pretreatment step). The hydrogen fluoride aqueous solution used had a volume ratio of hydrogen fluoride to DIW of 1:100.

[0169] Next, the substrate was removed from the hydrogen fluoride solution and immersed in a surface modification liquid for 10 minutes (surface modification process). The surface modification liquid used was SC-1 (volume ratio: ammonium water (NH3 concentration 28%): hydrogen peroxide water (H2O2 concentration 30%): DIW = 1:4:20).

[0170] On the other hand, a treatment liquid was also prepared separately from the surface modification process of the substrate. That is, in a sealed container in a stationary state, 100 ppm of water was added to toluene as an organic solvent under conditions of a temperature of 23°C and normal pressure. Furthermore, ultrasonic waves were applied to the mixture of toluene and water in a stationary state for 30 minutes. As a result, a dispersion liquid in which water was uniformly dispersed in toluene as a main solvent was prepared. The ultrasonic application conditions were a frequency of 45 Hz. Next, octadecyltrichlorosilane as a SAM forming material was added to the stationary dispersion liquid under conditions of a temperature of 23°C and normal pressure to prepare a treatment liquid (treatment liquid preparation process). The content (concentration) of octadecyltrichlorosilane was 5 mass% with respect to the total mass of the treatment liquid.

[0171] Next, the substrate was removed from the surface modification liquid and immersed in a treatment liquid containing a SAM-forming material for 5 minutes to form a SAM (thickness: about 1 nm) on the SiO2 film surface of the substrate (film formation step).

[0172] Next, the substrate was removed from the treatment solution and immersed in toluene as a removal solution for 1 minute to remove any unadsorbed SAM-forming material remaining on the substrate surface (removal step). Furthermore, the substrate was removed from the toluene and the surface on which the SAM was formed was dried by blowing nitrogen gas onto it (drying step). The temperature of the nitrogen gas was room temperature, and the drying time was 1 minute.

[0173] Next, the dried substrate was immersed in DIW to remove toluene (rinsing step), and then the surface on which the SAM was formed was dried by blowing nitrogen gas onto it (drying step). The temperature of the nitrogen gas was room temperature. In this way, a sample according to this embodiment was produced.

[0174] Next, the obtained sample was subjected to an etching process. Specifically, the substrate was immersed in an etching solution, and the area on the substrate surface that was not protected by the SAM was etched. The etching conditions were set to 195 seconds for immersion time in the etching solution (etching process time) so that the amount of SiO2 etched was about 10 nm. An aqueous hydrogen fluoride solution was used as the etching solution, and the volume ratio of hydrogen fluoride to DIW was hydrogen fluoride:DIW=1:100.

[0175] Next, the substrate was removed from the etching solution and immersed in DIW, and then removed from the DIW (rinsing process with DIW). The etched surface was then dried by spraying nitrogen gas on it (drying process). The temperature of the nitrogen gas was room temperature.

[0176] Example 2 In this example, the surface modification treatment for the substrate after the pretreatment step was changed to a method using ultraviolet light irradiation, except for that, samples were prepared in the same manner as in Example 1, and the obtained samples were subjected to an etching treatment.

[0177] The ultraviolet irradiation conditions were as follows: Light source for ultraviolet irradiation: Low pressure mercury lamp (product name: EUV200WS-51, manufactured by Sen Special Light Sources Co., Ltd.) UV peak wavelength: 185nm, 254nm UV irradiation intensity: 10mW / cm 2 UV exposure time: 15 minutes Pressure in the chamber: Atmospheric pressure Temperature inside the chamber: 23℃ Chamber atmosphere: air

[0178] Comparative Example 1 In this comparative example, the water content in the treatment solution was changed to 300 ppm, and the surface modification treatment for the substrate after the pretreatment step was changed to an annealing treatment. Other than that, samples were prepared in the same manner as in Example 1, and the obtained samples were subjected to an etching treatment.

[0179] The annealing conditions were a heating temperature of 600° C. and a heating time of 30 minutes. After the annealing process, the substrate was allowed to cool naturally until it reached room temperature.

[0180] Comparative Example 2 In this comparative example, the heating temperature in the annealing treatment was changed to 300° C. Except for that, a sample was prepared in the same manner as in Comparative Example 1, and the obtained sample was subjected to an etching treatment.

[0181] Comparative Example 3 In this comparative example, the substrate after the pretreatment step was not subjected to a surface modification treatment, but otherwise, a sample was prepared in the same manner as in Example 1, and the obtained sample was further subjected to an etching treatment.

[0182] Comparative Example 4 In this comparative example, instead of the surface modification liquid consisting of SC-1, hydrochloric acid hydrogen peroxide solution (SC-2) (volume ratio: hydrochloric acid (concentration 36%): hydrogen peroxide solution (concentration 30-36%): DIW = 1:1:5) was used. Except for that, samples were prepared in the same manner as in Example 1, and the obtained samples were subjected to an etching treatment.

[0183] Comparative Example 5 In this comparative example, nitric acid (volume ratio of nitric acid:DIW=1:3) was used instead of the surface modification liquid consisting of SC-1. Except for that, samples were prepared in the same manner as in Example 1, and the obtained samples were subjected to an etching treatment.

[0184] (SiOH / Si evaluation) For each sample according to Examples 1 and 2 and Comparative Examples 1 to 5, SiOH / Si was measured at two points by XPS analysis using an XPS measurement device (product name: Quantera SXM, manufactured by PHI Corporation) as the measurement device, and the average value was calculated. The results are shown in Table 1.

[0185] (SAM compactness evaluation) For each of the samples according to Examples 1 and 2 and Comparative Examples 1 to 5, the area ratio (%) of film defects in the SAM was calculated to evaluate the denseness of the SAM.

[0186] That is, the SAM of each sample was imaged using an atomic force microscope (AFM) (trade name: Dimension Icon, manufactured by Bruker Japan Co., Ltd.), and an observation image (AFM image) of 500 nm square was obtained. Next, each obtained observation image was binarized, and then image processing was performed to map the film defects, and the site (region) of the film defect of the SAM was identified. In order to identify the site (region) of the film defect of the SAM by mapping, image processing was performed so that defects located at a depth of less than 1 nm from the SAM surface were mapped, taking into consideration that the film thickness of the SAM was about 1 nm. This ensured that the site (region) at a depth of more than 1 nm from the SAM surface, more specifically, the etched site, was not mapped as the region of the film defect of the SAM and was not included in the area. Next, the area of ​​the film defect region of the SAM identified by image processing was calculated, and the ratio to the area of ​​the entire region in the observation image was calculated. The results are shown in Table 1.

[0187] (result) As can be seen from Table 1, in Example 1 in which surface modification was performed using SC-1 as the surface modification liquid, and in Example 2 in which surface modification was performed by ultraviolet irradiation, it was confirmed that the value of SiOH / Si was increased compared to Comparative Example 3 in which no surface modification treatment was performed. On the other hand, in Comparative Examples 1 and 2 in which surface modification was performed by annealing treatment, Comparative Example 4 in which surface modification was performed using SPM as the surface modification liquid, and Comparative Example 5 in which surface modification was performed using nitric acid as the surface modification liquid, it was confirmed that the value of SiOH / Si was unchanged or decreased compared to Comparative Example 3. As a result, it was confirmed that when the surface modification treatment was performed using SC-1 as the surface modification liquid or when the surface modification treatment was performed by ultraviolet irradiation, hydroxyl groups could be well imparted to the SiO2 layer.

[0188] Furthermore, the area ratios (%) of the film defects in the SAM in Examples 1 and 2 were 10.7% and 10.0%, respectively, which were reduced compared to Comparative Example 3 in which no surface modification treatment was performed, and Comparative Examples 1, 2, 4, and 5 in which surface modification treatment was performed by other methods. This confirmed that the SAMs in Examples 1 and 2 all had good density and protective performance.

[0189] [Table 1] [Explanation of symbols]

[0190] 1 SiO2 layer (protected layer) 2 SiN layer (layer to be etched) 3. Laminate 4. Memory Trench 5 SAM (self-assembled monolayer) molecule 6 SAM (Self-assembled monolayer) 100 Semiconductor manufacturing equipment 110 Board holding part 120 Pre-treatment liquid supply unit 121 Pretreatment liquid storage section 130 Surface modification liquid supply unit 131 Surface modification liquid storage section 140 Processing liquid supply unit 141 Processing liquid storage section 144 Organic Solvent Supply Section 145 Water supply section 146 SAM forming material supply section 150 Removal liquid supply section 151 Removal fluid storage section 160 Etching solution supply unit 161 Etching solution storage section 190 Swivel drive unit 200 Substrate Processing Unit 210 Ultraviolet irradiation unit 220 Lifter 230 Treatment tank 231 Injection tube 232 Inner tank 233 Outer tank 300 Control section S1 SAM (self-assembled monolayer) formation process S2, S2' Etching process S101 Pretreatment process S102, S102' Surface modification process S103 Processing solution preparation process S104 Film formation process S105 Removal process S106 Drying process W substrate Wf substrate surface

Claims

1. A substrate processing method for forming a self-assembled monolayer on a surface of a substrate, comprising the steps of: a surface modification step of modifying the surface of the substrate by adding hydroxyl groups; a film formation step of contacting a treatment liquid containing molecules capable of forming the self-assembled monolayer with the surface of the substrate after the surface modification step to form the self-assembled monolayer; Including, the molecule has a functional group capable of undergoing a dehydration condensation reaction with the hydroxyl group, the film-forming step is a step of chemically adsorbing the molecule onto the surface of the substrate through a dehydration condensation reaction between the hydroxyl group and the functional group of the molecule; A method for processing a substrate.

2. 2. The substrate processing method according to claim 1, wherein the surface modification step is a step of bringing a surface modification liquid made of an alkaline solution into contact with the surface of the substrate.

3. 3. The substrate processing method according to claim 2, wherein the alkaline solution is an ammonia-hydrogen peroxide solution mixture, ammonia water, a tetramethylammonium hydroxide solution, or a trimethyl-2-hydroxyethylammonium hydroxide solution.

4. 2. The substrate processing method according to claim 1, wherein the surface modification step is a step of irradiating the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms.

5. The substrate processing method according to claim 1 , further comprising a pretreatment step of contacting the surface of the substrate with a pretreatment liquid containing hydrogen fluoride before the surface modification step.

6. 1. A method for manufacturing a semiconductor device, comprising processing a substrate having a laminate provided on a surface thereof, the method comprising: The laminate includes a layer to be protected from etching and a layer to be etched that are alternately laminated, selectively forming a self-assembled monolayer on at least a surface of the layer to be protected; selectively etching the layer to be etched using the self-assembled monolayer as a protective layer; Including, The step of forming a self-assembled monolayer includes: a surface modification step of modifying the surface of the protective layer by adding hydroxyl groups; a film forming step of contacting the surface of the protective layer after the surface modification step with a treatment liquid containing molecules capable of forming the self-assembled monolayer to form the self-assembled monolayer; Including, the molecule has a functional group capable of undergoing a dehydration condensation reaction with the hydroxyl group, the film-forming step is a step of chemically adsorbing the molecule onto the surface of the layer to be protected by a dehydration condensation reaction between the hydroxyl group and the functional group of the molecule; A method for manufacturing a semiconductor device.

7. 7. The method for manufacturing a semiconductor device according to claim 6, wherein the surface modification step is a step of bringing a surface modification liquid made of an alkaline solution into contact with the surface of the layer to be protected.

8. 8. The method for manufacturing a semiconductor device according to claim 7, wherein the alkaline solution is an ammonia-hydrogen peroxide solution mixture, ammonia water, a tetramethylammonium hydroxide solution, or a trimethyl-2-hydroxyethylammonium hydroxide solution.

9. 7. The method for manufacturing a semiconductor device according to claim 6, wherein the surface modification step is a step of irradiating the surface of the layer to be protected with ultraviolet light in an atmosphere containing oxygen atoms.

10. 7. The method for manufacturing a semiconductor device according to claim 6, further comprising a pretreatment step of contacting the surface of the layer to be protected with a pretreatment liquid containing hydrogen fluoride before the surface modification step.

11. A substrate processing apparatus for forming a self-assembled monolayer on a surface of a substrate, comprising: a surface modification unit that modifies the surface of the substrate by adding hydroxyl groups; a treatment liquid supply unit that supplies a treatment liquid containing molecules capable of forming the self-assembled monolayer to the surface of the substrate that has been surface-modified by the surface modification unit, thereby forming the self-assembled monolayer; Equipped with the molecule has a functional group capable of undergoing a dehydration condensation reaction with the hydroxyl group, the processing liquid supply unit chemically adsorbs the molecule onto the surface of the substrate through a dehydration condensation reaction between the hydroxyl group and the functional group of the molecule; Substrate processing equipment.

12. The substrate processing apparatus according to claim 11 , wherein the surface modifying unit is a surface modifying liquid supply unit that supplies a surface modifying liquid made of an alkaline solution to the surface of the substrate.

13. 13. The substrate processing apparatus according to claim 12, wherein the alkaline solution is an ammonia-hydrogen peroxide solution mixture, ammonia water, a tetramethylammonium hydroxide aqueous solution, or a trimethyl-2-hydroxyethylammonium hydroxide aqueous solution.

14. The substrate processing apparatus according to claim 11 , wherein the surface modification unit is an ultraviolet irradiating unit that irradiates the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms.

15. The substrate processing apparatus according to claim 11 , further comprising a pre-treatment liquid supplying unit that supplies a pre-treatment liquid containing hydrogen fluoride to the surface of the substrate before the surface is modified by the surface modifying unit.

16. A semiconductor manufacturing apparatus for processing a substrate having a laminate on a surface thereof, comprising: The laminate includes a layer to be protected from etching and a layer to be etched which are alternately laminated, a surface modification unit that modifies the surface of the protective layer by adding hydroxyl groups; a treatment liquid supply unit that supplies a treatment liquid containing molecules capable of forming a self-assembled monolayer to the surface of the protection layer that has been surface-modified by the surface modification unit, thereby forming the self-assembled monolayer; an etching unit that selectively etches and removes the layer to be etched using the self-assembled monolayer as a protective layer; Equipped with the molecule has a functional group capable of undergoing a dehydration condensation reaction with the hydroxyl group, the processing liquid supply unit chemically adsorbs the molecule onto the surface of the layer to be protected by a dehydration condensation reaction between the hydroxyl group and the functional group of the molecule; Semiconductor manufacturing equipment.

17. A semiconductor manufacturing apparatus for processing a substrate having a laminate on a surface thereof, comprising: The laminate includes a layer to be protected from etching and a layer to be etched that are alternately laminated, a substrate processing unit for selectively forming a self-assembled monolayer on at least a surface of the layer to be protected; an etching processing unit that selectively etches and removes the layer to be etched using the self-assembled monolayer as a protective layer; Equipped with The substrate processing unit includes: a surface modification unit that modifies the surface of the protective layer by adding hydroxyl groups; a treatment liquid supply unit that supplies a treatment liquid containing molecules capable of forming the self-assembled monolayer to the surface of the protection layer that has been surface-modified by the surface modification unit, thereby forming the self-assembled monolayer; Equipped with the molecule has a functional group capable of undergoing a dehydration condensation reaction with the hydroxyl group, the processing liquid supply unit chemically adsorbs the molecule onto the surface of the layer to be protected by a dehydration condensation reaction between the hydroxyl group and the functional group of the molecule; Semiconductor manufacturing equipment.

18. 18. The semiconductor manufacturing apparatus according to claim 16, wherein the surface modifying unit is a surface modifying liquid supply unit that supplies a surface modifying liquid made of an alkaline solution to the surface of the layer to be protected.

19. 19. The semiconductor manufacturing apparatus according to claim 18, wherein the alkaline solution is an ammonia-hydrogen peroxide solution mixture, ammonia water, a tetramethylammonium hydroxide aqueous solution, or a trimethyl-2-hydroxyethylammonium hydroxide aqueous solution.

20. 18. The semiconductor manufacturing apparatus according to claim 16, wherein the surface modification unit is an ultraviolet irradiating unit that irradiates the surface of the layer to be protected with ultraviolet light in an atmosphere containing oxygen atoms.

21. 18. The semiconductor manufacturing apparatus according to claim 16, further comprising a pretreatment liquid supplying section that supplies a pretreatment liquid containing hydrogen fluoride to the surface of the layer to be protected before the surface is modified by the surface modifying section.

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