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

Abstract

The invention provides a substrate processing method, a substrate processing apparatus, a method of manufacturing a semiconductor device, and a semiconductor manufacturing apparatus, wherein a self-assembled monomolecular film having excellent compactness and protection performance can be efficiently formed on the surface of a substrate in a short time by suppressing or reducing the occurrence of film defects. This substrate processing method forms SAM on the surface (Wf) of a substrate (W), and comprises: a surface modification step (S102) in which SAM can be formed by surface modification on the surface (Wf) of the substrate (W); a first contact step (S104) in which SAM is formed by bringing a first treatment liquid containing first molecules (5) capable of forming SAM into contact with the surface (Wf) of the substrate (W) after the surface modification step (S102); and a second contact step (S106) in which a second treatment liquid containing second molecules (8) of the same type or different types as the first molecules (5) is brought into contact with the surface (Wf) of the substrate (W) after the first contact step (S104), and the second molecules (8) are chemically adsorbed to the region where SAM is not formed. The second contact step (S106) is performed at least once until the area ratio (%) of film defects of the SAM formed on the surface (Wf) of the substrate (W) is equal to or less than an arbitrarily set threshold value.

Description

TECHNICAL FIELD

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

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

[0003] However, in recent years, semiconductor devices are increasingly miniaturized, and in terms of the photolithography technique, there are cases where the positioning accuracy is insufficient. Therefore, a method for selectively forming a film on a specific region of a substrate surface with high accuracy is required instead of the photolithography technique.

[0004] For example, in Patent Literature 1, a method for selectively etching a silicon nitride (SiN) film by previously forming a heat-resistant phosphoric material as a SAM on the surface of a silicon oxide (SiO2) film on a substrate provided with the silicon nitride film and the silicon oxide film in-plane is disclosed.

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

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

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

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] The present application has been achieved in view of the above-described problems, and an object thereof is to provide a substrate processing method and a substrate processing apparatus capable of efficiently forming a self-assembled monolayer film having excellent denseness and protection performance on a substrate surface in a short time by suppressing or reducing the generation of film defects, and a semiconductor device manufacturing method and a semiconductor manufacturing apparatus.

[0011] MEANS OF SOLVING THE PROBLEM

[0012] To solve the above problems, a substrate processing method according to the present application is characterized by being a substrate processing method of forming a self-assembled monomolecular film on a surface of a substrate, the substrate processing method including: a surface modification step of performing surface modification on the surface of the substrate to enable formation of the self-assembled monomolecular film; a first contact step of bringing a first processing liquid containing a first molecule capable of forming the self-assembled monomolecular film into contact with the surface of the substrate after the surface modification step to form the self-assembled monomolecular film; and a second contact step of bringing a second processing liquid containing a second molecule of the same kind or a different kind from the first molecule into contact with the surface of the substrate after the first contact step to chemisorb the second molecule to a region where the self-assembled monomolecular film is not formed; the second contact step being performed at least once until an area ratio (%) of film defects of the self-assembled monomolecular film formed on the surface of the substrate reaches below an arbitrarily set threshold value.

[0013] According to the above structure, first, in the surface modification step, surface modification capable of forming a self-assembled monomolecular film (hereinafter, sometimes referred to as "SAM") is performed on the surface of the substrate. Next, in the first contact step, a first processing liquid containing a first molecule capable of forming a SAM is brought into contact with the surface of the substrate after the surface modification. Thereby, the first molecule is chemisorbed to the surface of the substrate to form a SAM by self-assembly. Here, in the SAM formed in the first contact step, there are cases where film defects occur locally due to the first molecule being unable to be chemisorbed to the surface of the substrate or the like. Especially in a case where the contact time of the first molecule with the surface of the substrate is short, the frequency of occurrence of film defects in-plane increases, or the area of film defects becomes large. However, in the above structure, in the second contact step, a second processing liquid containing a second molecule of the same kind or a different kind from the first molecule is brought into contact with the surface of the substrate after the first contact step. Thereby, the second molecule is chemisorbed to a region where a SAM is not formed, thereby reducing or repairing film defects of the SAM. In addition, the second contact step is performed at least once until the area ratio (%) of film defects of the SAM reaches below an arbitrarily set threshold value. Therefore, in the above structure, even if the SAM molecule is not brought into contact with the surface of the substrate for a long time in order to form a dense SAM as in the conventional substrate processing method, it is possible to suppress the occurrence of film defects and to efficiently form a SAM excellent in density and protective performance in a short time.

[0014] In the above structure, the second molecule is preferably a molecule having a molecular chain length that is the same as or shorter than that of the first molecule. Thereby, it is possible to prevent or reduce the second molecule from becoming unable to be chemisorbed due to steric hindrance between the second molecule and the first molecule that has been adsorbed to the surface of the substrate when the second molecule is chemisorbed to the surface of the substrate. As a result, it is possible to further reduce or repair film defects of the SAM, thereby making it possible to form a SAM excellent in density and protective performance.

[0015] Further, in the above structure, in a case where the second contact process is performed plural times, the second molecule used in a process performed first is preferably a second molecule having the same or longer molecular chain length than a second molecule used in a process performed later. Thus, even in a case where the second contact process is performed plural times, it is possible to prevent or reduce the second molecule to be chemisorbed in a process performed later from becoming unable to be chemisorbed due to steric hindrance between the first molecule or the second molecule already chemisorbed on the surface of the substrate. As a result, it is possible to further reduce or repair film defects of the SAM, and to form a SAM having excellent denseness and protection performance.

[0016] Further, in the above structure, it is preferable that the first molecule and the second molecule have a functional group capable of performing a dehydration condensation reaction with a hydroxyl group, the surface modification process is a process of imparting the hydroxyl group to the surface of the substrate, and the first contact process and the second contact process are processes of chemisorbing the first molecule or the second molecule to the surface of the substrate by dehydration condensation reaction of the functional group possessed by the first molecule or the second molecule with the hydroxyl group of the surface of the substrate.

[0017] Further, in the above structure, the surface modification process can be a process of bringing a surface modification liquid containing an alkaline solution into contact with the surface of the substrate, or a process of irradiating ultraviolet rays to the surface of the substrate in an atmosphere containing oxygen atoms, thereby imparting the hydroxyl group to the surface of the substrate. Thus, it is possible to perform introduction of the hydroxyl group in the surface modification process. As a result, it is possible to chemisorb the SAM molecules to the surface of the substrate at a higher density, and to form a SAM having more excellent denseness and protection performance.

[0018] To solve the above problems, the manufacturing method of a semiconductor device according to the present application is characterized by including a process of a substrate provided with a laminate on a surface, the laminate including a protected layer to be a protection target of etching and a structure in which an etched layer to be a target of etching is alternately laminated, the manufacturing method of a semiconductor device 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 with the self-assembled monolayer as a protection layer, the step of forming the self-assembled monolayer including a surface modification step of performing surface modification on a surface of the protected layer to enable formation of the self-assembled monolayer, a first contact step of bringing a first treatment liquid including a first molecule enabling formation of the self-assembled monolayer into contact with the surface of the protected layer after the surface modification step to form the self-assembled monolayer, and a second contact step of bringing a second treatment liquid including a second molecule of the same kind or a different kind from the first molecule into contact with the surface of the substrate after the first contact step to chemically adsorb the second molecule to a region where the self-assembled monolayer is not formed, the second contact step being performed at least once until an area ratio (%) of a film defect of the self-assembled monolayer formed on the surface of the protected layer reaches a threshold value or less.

[0019] According to the above structure, first, in the surface modification step, surface modification enabling formation of a SAM is performed on the surface of the protected layer. Next, in the first contact step, a first treatment liquid including a first molecule enabling formation of a SAM is brought into contact with the surface of the protected layer after the surface modification. Thereby, the first molecule is chemically adsorbed to the surface of the protected layer to self-assemble and form a SAM. Here, in the SAM formed in the first contact step, there are cases where a film defect occurs locally in that the first molecule cannot be chemically adsorbed to the surface of the protected layer or the like. Especially in a case where the contact time of the first molecule with the surface of the protected layer is short, the frequency of occurrence of the film defect in-plane increases, or the area of the film defect becomes large. However, in the above configuration, in the second contact step, a second treatment liquid including a second molecule of the same kind or a different kind from the first molecule is brought into contact with the surface of the protected layer after the first contact step. Thereby, the second molecule is chemically adsorbed to a region where the SAM is not formed, thereby reducing or repairing the film defect of the SAM. In addition, the second contact step is performed at least once until the area ratio (%) of the film defect of the SAM reaches a threshold value or less. Therefore, according to the above configuration, even if the SAM molecule is not brought into contact with the surface of the protected layer for a long time in order to form a dense SAM as in the conventional manufacturing method of a semiconductor device, it is possible to suppress the occurrence of the film defect, and it is possible to efficiently form a SAM having excellent denseness and protection performance in a short time.

[0020] In the above structure, the second molecule is preferably one having a molecular chain length that is the same as or shorter than that of the first molecule. Thus, it is possible to prevent or reduce the second molecule from becoming unable to chemically adsorb due to steric hindrance between the first molecules that have already chemically adsorbed to the surface of the protective layer when the second molecule chemically adsorbs to the surface of the protective layer. As a result, it is possible to further reduce or repair film defects of the SAM, and thus to form a SAM that is excellent in density and protective performance.

[0021] Further, in the above structure, in a case where the second contact process is performed a plurality of times, the second molecule used in a process performed first is preferably one having a molecular chain length that is the same as or longer than that of the second molecule used in a process performed later. Thus, even in a case where the second contact process is performed a plurality of times, it is possible to prevent or reduce the second molecule to be chemically adsorbed in a process performed later from becoming unable to chemically adsorb due to steric hindrance between the first molecules or the second molecules that have already chemically adsorbed to the surface of the protective layer. As a result, it is possible to further reduce or repair film defects of the SAM, and thus to form a SAM that is excellent in density and protective performance.

[0022] In addition, in the above structure, it is preferable that the first molecule and the second molecule have a functional group capable of undergoing a dehydration condensation reaction with a hydroxyl group, the surface modification process is a process of imparting the hydroxyl group to the surface of the protective layer, and the first contact process and the second contact process are processes of causing the first molecule or the second molecule to chemically adsorb to the surface of the protective layer by a dehydration condensation reaction of the functional group possessed by the first molecule or the second molecule with the hydroxyl group of the surface of the protective layer.

[0023] Further, in the above structure, the surface modification process can be a process of bringing a surface modification liquid containing an alkaline solution into contact with the surface of the substrate or irradiating ultraviolet rays to the surface of the substrate in an atmosphere containing oxygen, thereby imparting the hydroxyl group to the surface of the substrate. Thus, it is possible to perform introduction of the hydroxyl group well in the surface modification process. As a result, it is possible to cause the SAM molecules to chemically adsorb to the surface of the protective layer at a higher density, and thus to form a SAM that is more excellent in density and protective performance.

[0024] To solve the above problems, a substrate processing apparatus according to the present application is characterized in that a self-assembled monolayer is formed on a surface of a substrate, the substrate processing apparatus includes a surface modification section that performs surface modification on the surface of the substrate to enable formation of the self-assembled monolayer, and a first processing liquid supply section that supplies a first processing liquid containing a first molecule that enables formation of the self-assembled monolayer to the surface of the substrate that has been surface-modified by the surface modification section, thereby forming the self-assembled monolayer, and the second processing liquid supply section supplies the second processing liquid at least once until the area ratio (%) of film defects of the self-assembled monolayer formed on the surface of the substrate reaches an arbitrarily set threshold value or less.

[0025] According to the above structure, the surface modification section performs surface modification on the surface of the substrate, thereby enabling formation of the SAM. In addition, the first processing liquid supply section enables the first molecule to chemisorb by supplying the first processing liquid containing the first molecule that enables formation of the SAM to the surface of the substrate after surface modification, thereby forming the SAM. Here, in the SAM formed on the surface of the substrate, there are cases where film defects occur locally in which the first molecule cannot chemisorb to the surface of the substrate or the like. In particular, in a case where the contact time of the first molecule with the surface of the substrate is short, the frequency of occurrence of film defects in the plane increases, or the area of film defects becomes large. However, in the above structure, the second processing liquid supply section supplies a second processing liquid containing a second molecule of the same kind or a different kind from the first molecule to the surface of the substrate. Thereby, the second molecule also chemisorbs to the region where the SAM is not formed, thereby enabling reduction or repair of film defects of the SAM. In addition, the second processing liquid supply section performs supply of the second processing liquid at least once until the area ratio (%) of film defects of the SAM reaches an arbitrarily set threshold value or less. Therefore, according to the above structure, even if the SAM molecule does not contact the surface of the substrate for a long time in order to form a dense SAM as in the conventional substrate processing apparatus, it is possible to suppress the occurrence of film defects, thereby enabling formation of a SAM that is excellent in density and protective performance in a short time with high efficiency.

[0026] In the above structure, the second molecule can be configured to have a molecular chain length that is the same as or shorter than that of the first molecule. Thereby, it is possible to prevent or reduce the second molecule from becoming unable to chemisorb due to steric hindrance between the second molecule and the first molecule that has already chemisorbed to the surface of the substrate when the second molecule chemisorbs to the surface of the substrate. As a result, it is possible to further reduce or repair film defects of the SAM, thereby enabling formation of a SAM that is excellent in density and protective performance.

[0027] Further, in the above structure, in a case where the second processing liquid is supplied to the surface of the substrate multiple times by the second processing liquid supply section, the second molecules included in the second processing liquid supplied first preferably have the same or longer molecular chain length as the second molecules included in the second processing liquid supplied later. Thus, even in a case where the second processing liquid is supplied multiple times by the second processing liquid supply section, the second molecules to be chemisorbed in a process performed later can be prevented or reduced from becoming unable to be chemisorbed due to steric hindrance between the first molecules or the second molecules already chemisorbed on the surface of the substrate. As a result, the film defect of the SAM can be further reduced or repaired, and thus a SAM having excellent denseness and protection performance can be formed.

[0028] Further, in the above structure, it is preferable that the first molecules and the second molecules have a functional group capable of undergoing a dehydration condensation reaction with a hydroxyl group, the surface modification section performs the surface modification by imparting the hydroxyl group to the surface of the substrate, and the first processing liquid supply section and the second processing liquid supply section cause the first molecules or the second molecules to be chemisorbed to the surface of the substrate by a dehydration condensation reaction of the functional group possessed by the first molecules or the second molecules with the hydroxyl group of the surface of the substrate.

[0029] Further, in the above structure, the surface modification section is preferably a surface modification liquid supply section that imparts a hydroxyl group to the surface of the substrate by supplying a surface modification liquid containing an alkaline solution to the surface of the substrate, or is preferably an ultraviolet irradiation section that imparts a hydroxyl group to the surface of the substrate by irradiating ultraviolet rays to the surface of the substrate in an atmosphere containing oxygen atoms. The surface modification liquid supply section or the ultraviolet irradiation section can introduce more hydroxyl groups to the surface of the substrate. As a result, more SAM molecules can be chemisorbed to the surface of the substrate, and thus a SAM having excellent denseness and protection performance can be formed.

[0030] To solve the above problems, a semiconductor manufacturing apparatus according to the present application is characterized by performing processing of a substrate provided with a laminate on a surface, the laminate including a protected layer to be a protection target of etching and a structure in which an etched layer to be a target of etching is alternately laminated, and the semiconductor manufacturing apparatus includes a surface modification section that performs surface modification on the surface of the protected layer to enable formation of a self-assembled monolayer; a first processing liquid supply section that supplies a first processing liquid including a first molecule capable of forming the self-assembled monolayer to the surface of the protected layer on which surface modification is performed by the surface modification section, thereby forming the self-assembled monolayer; a second processing liquid supply section that supplies a second processing liquid including a second molecule of the same kind or a different kind from the first molecule to the surface of the protected layer on which the self-assembled monolayer is formed, thereby causing the second molecule to chemisorb to a region in which the self-assembled monolayer is not formed; and an etching section that selectively etches and removes the etched layer with the self-assembled monolayer as a protection layer, and the second processing liquid supply section performs supply of the second processing liquid at least once until an area ratio (%) of a film defect of the self-assembled monolayer formed on the surface of the protected layer reaches an arbitrarily set threshold value or less.

[0031] The semiconductor manufacturing apparatus of the above structure can achieve excellent selective etching of the etched layer by forming a SAM on at least the surface of the protected layer in advance to protect it before etching the etched layer. In the above structure, the surface modification section performs surface modification on the surface of the protected layer, thereby enabling formation of the SAM. In addition, the first processing liquid supply section supplies the first processing liquid including the first molecule capable of forming the SAM to the surface of the protected layer after surface modification, thereby enabling the first molecule to chemisorb to form the SAM. Here, in the SAM formed on the surface of the protected layer, there are cases in which a film defect occurs locally in which the first molecule cannot chemisorb to the surface of the protected layer or the like. In particular, in a case in which the contact time of the first molecule with the surface of the protected layer is short, the frequency of occurrence of the film defect in-plane increases, or the area of the film defect becomes large. However, in the above structure, the second processing liquid supply section supplies the second processing liquid including the second molecule of the same kind or a different kind from the first molecule to the surface of the protected layer. Thereby, the second molecule also chemisorbs to a region in which the SAM is not formed, thereby enabling reduction or repair of the film defect of the SAM. In addition, the second processing liquid supply section performs supply of the second processing liquid at least once until the area ratio (%) of the film defect of the SAM reaches an arbitrarily set threshold value or less. Therefore, with the above structure, even without making the SAM molecules contact the surface of the protected layer for a long time in order to form a dense SAM as in the conventional semiconductor manufacturing apparatus, it is possible to suppress occurrence of the film defect, thereby enabling formation of a SAM that is excellent in density and protection performance with high efficiency in a short time.

[0032] To solve the above problems, a semiconductor manufacturing apparatus according to the present application is characterized by performing processing of a substrate provided with a laminate on a surface, the laminate including a protected layer to be a protection target of etching and a structure alternately laminated with an etched layer to be a target of etching, the semiconductor manufacturing apparatus having: a substrate processing unit that selectively forms a self-assembled monolayer on at least a surface of the protected layer; and an etching processing unit that selectively etches and removes the etched layer with the self-assembled monolayer as a protection layer, the substrate processing unit having: a surface modification section that performs surface modification on a surface of the protected layer to enable formation of the self-assembled monolayer; a first processing liquid supply section that supplies a first processing liquid containing a first molecule enabling formation of the self-assembled monolayer to a surface of the protected layer on which surface modification is performed by the surface modification section, thereby forming the self-assembled monolayer; and a second processing liquid supply section that supplies a second processing liquid containing a second molecule of the same kind or a different kind from the first molecule to a surface of the protected layer on which the self-assembled monolayer is formed, thereby causing the second molecule to chemisorb to a region on which the self-assembled monolayer is not formed, the second processing liquid supply section supplying the second processing liquid at least once until an area ratio (%) of a film defect of the self-assembled monolayer formed on the surface of the protected layer reaches an arbitrarily set threshold value or less.

[0033] The semiconductor manufacturing apparatus of the above structure has at least a substrate processing unit that selectively forms a SAM on a protective layer, and an etching processing unit that selectively etches and removes an etching layer, in which a SAM is formed on at least the surface of the protective layer in the substrate processing unit to protect it before etching the etching layer, thereby enabling excellent selective etching of the etching layer. In the above structure, the surface modification unit performs surface modification on the surface of the protective layer, thereby enabling formation of a SAM. In addition, the first treatment liquid supply unit supplies a first treatment liquid containing a first molecule capable of forming a SAM to the surface of the protective layer after surface modification, thereby enabling chemical adsorption of the first molecule to form a SAM. Here, in the SAM formed on the surface of the protective layer, there are cases where a film defect occurs in which SAM molecules cannot be chemically adsorbed to the surface of the protective layer, and the like. In particular, in a case where the contact time of the SAM molecules with the surface of the protective layer is short, the frequency of occurrence of film defects in the plane increases, or the area of the film defects becomes large. However, in the above structure, the second treatment liquid supply unit supplies a second treatment liquid containing a second molecule of the same kind or a different kind from the first molecule to the surface of the protective layer. Thereby, the second molecule can also be chemically adsorbed to the area where the SAM is not formed, thereby reducing or repairing the film defects of the SAM. In addition, the second treatment liquid supply unit supplies the second treatment liquid at least once until the area ratio (%) of the film defects of the SAM reaches an arbitrarily set threshold value or less. Therefore, for the above structure, even if the SAM molecules are not brought into contact with the surface of the protective layer for a long time in order to form a dense SAM as in the conventional semiconductor manufacturing apparatus, the occurrence of film defects can be suppressed, and a SAM having excellent density and protection performance can be efficiently formed in a short time.

[0034] In the above structure, the second molecule can be configured to have the same or shorter molecular chain length than the first molecule. According to the above structure, the surface modification liquid supply unit supplies a surface modification liquid containing an alkaline solution to the surface of the protective layer, thereby enabling the surface of the protective layer to be imparted with a hydroxyl group. Thereby, the area where the SAM molecules having a hydroxyl group cannot be chemically adsorbed can be greatly reduced, and more SAM molecules can be chemically adsorbed to the surface of the protective layer at a high density. As a result, a SAM having excellent density and protection performance can be formed.

[0035] Further, in the above structure, in a case where the second treatment liquid supply section supplies the second treatment liquid to the surface of the protective layer a plurality of times, the second molecules included in the second treatment liquid supplied first preferably have a molecular chain length that is the same as or longer than the second molecules included in the second treatment liquid supplied later. Thus, even in a case where the second treatment liquid supply section supplies the second treatment liquid a plurality of times, it is possible to prevent or reduce second molecules to be chemisorbed in a process performed later from becoming unable to be chemisorbed due to steric hindrance between the first molecules or the second molecules that have already been chemisorbed to the surface of the protective layer. As a result, it is possible to further reduce or repair defects of the SAM, and thus it is possible to form a SAM that is excellent in density and protective performance.

[0036] Further, in the above structure, it is preferable that the first molecules and the second molecules have a functional group capable of undergoing a dehydration condensation reaction with a hydroxyl group, the surface modification section performs the surface modification by imparting the hydroxyl group to the surface of the substrate, and the first treatment liquid supply section and the second treatment liquid supply section cause the first molecules or the second molecules to be chemisorbed to the surface of the substrate by a dehydration condensation reaction of the functional group possessed by the first molecules or the second molecules with the hydroxyl group of the surface of the substrate.

[0037] Further, in the above structure, the surface modification section is preferably a surface modification liquid supply section that imparts a hydroxyl group to the surface of the protective layer by supplying a surface modification liquid including an alkaline solution to the surface of the protective layer, or is preferably an ultraviolet irradiation section that imparts a hydroxyl group to the surface of the protective layer by irradiating ultraviolet rays to the surface of the substrate in an atmosphere including an oxygen atom. The surface modification liquid supply section or the ultraviolet irradiation section can introduce more hydroxyl groups to the surface of the protective layer. As a result, it is possible to cause more SAM molecules to be chemisorbed to the surface of the protective layer, and thus it is possible to form a SAM that is excellent in density and protective performance.

[0038] Effects of Invention

[0039] According to the present application, it is possible to provide a substrate processing method and a substrate processing apparatus, and a semiconductor device manufacturing method and a semiconductor manufacturing apparatus, in which a self-assembled monolayer film that is excellent in density and protective performance is formed on a substrate surface in a short time with high efficiency, and in which generation of defects of the film is inhibited or reduced. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 (a) is a cross-sectional view schematically showing a laminate provided on a substrate, showing a state before an etching process.

[0041] Figure 1(b) is a sectional view schematically showing a laminate provided on a substrate, showing a case after an etching process.

[0042] Figure 2 (a) is Figure 1 (a) is a partial enlarged view of a portion of the laminate surrounded by A.

[0043] Figure 2 (b) is a partial enlarged view showing a case where a SAM is formed on the surface of the SiO2 layer.

[0044] Figure 2 (c) is Figure 1 (b) is a partial enlarged view of a portion of the laminate surrounded by B, showing a case where the SiN layer is etched.

[0045] Figure 3 is a flowchart showing an example of the overall flow of the manufacturing method of the semiconductor device of the first embodiment of the present application.

[0046] Figure 4 (a) is an explanatory diagram conceptually showing the surface state of the SiO2 layer before surface modification in the first embodiment.

[0047] Figure 4 (b) is an explanatory diagram conceptually showing the surface state of the SiO2 layer after surface modification.

[0048] Figure 4 (c) is an explanatory diagram showing a case where the first treatment liquid is supplied to the surface of the SiO2 layer.

[0049] Figure 5 (a) is an explanatory diagram showing a case where the first molecule is chemisorbed to the surface of the SiO2 layer.

[0050] Figure 5 (b) is an explanatory diagram showing a case where the first molecule self-assembles on the surface of the SiO2 layer to form a SAM.

[0051] Figure 5 (c) is an explanatory diagram showing a case where the second treatment liquid is supplied to the surface of the SiO2 layer.

[0052] Figure 6 is an explanatory diagram showing the state of the SAM after the densification process.

[0053] Figure 7 is an explanatory diagram showing the schematic structure of the semiconductor manufacturing apparatus of the first embodiment of the present application.

[0054] Figure 8 is an explanatory diagram showing the schematic structure of the pretreatment liquid storage portion in the pretreatment liquid supply portion of the semiconductor manufacturing apparatus of the first embodiment of the present application.

[0055] Figure 9 is an explanatory diagram showing a schematic structure of a surface modification liquid storage section provided in a surface modification liquid supply section in a semiconductor manufacturing apparatus according to the first embodiment of the present application.

[0056] Figure 10 is an explanatory diagram showing a schematic structure of a first processing liquid storage section in a first processing liquid supply section and an ultrasonic wave application section in a semiconductor manufacturing apparatus according to the first embodiment of the present application.

[0057] Figure 11 is an explanatory diagram showing a schematic structure of an etching liquid storage section in an etching liquid supply section according to the first embodiment of the present application.

[0058] Figure 12 is a flowchart showing an example of an overall flow of a semiconductor device manufacturing method according to the second embodiment of the present application.

[0059] Figure 13 is an explanatory diagram showing a schematic structure of a semiconductor manufacturing apparatus according to the second embodiment of the present application.

[0060] Figure 14 is a side view showing a schematic structure of a lifter in a semiconductor manufacturing apparatus according to the second embodiment of the present application.

[0061] Figure 15 is a cross-sectional view showing a case where a plurality of substrates on which SAMs are formed are immersed in an etching liquid according to the second embodiment of the present application. DETAILED DESCRIPTION

[0062] (First Embodiment)

[0063] The first embodiment of the present application will be described below.

[0064] [Substrate processing method (semiconductor device manufacturing method)]

[0065] First, the substrate processing method according to the present embodiment will be described below with reference to the accompanying drawings.

[0066] The substrate processing method according to the present embodiment provides, for example, a technology capable of achieving a good selective etching when forming a three-dimensional structure such as a three-dimensional NAND structure on a substrate surface.

[0067] The substrate processing method according to the present embodiment can be applied to a part of a process of forming a three-dimensional NAND structure on a substrate W containing silicon or the like. Therefore, the following describes an example in which the substrate processing method according to the present embodiment is applied to a semiconductor device manufacturing method, more specifically, to a process of forming a three-dimensional NAND structure on a substrate W provided with a memory cell array including a plurality of memory cells each including a vertical NAND structure. Figure 1The processing of the substrate W of the laminate 3 shown in the three-dimensional structure will be illustrated as an example. Figure 1 (a) is a schematic cross-sectional view of a laminate disposed on a substrate W, showing the state before the etching process. Figure 1 (b) is a schematic cross-sectional view of the laminate disposed on the substrate W, showing the situation after the etching process.

[0068] like Figure 2 As shown in (a), the laminate 3 comprises a structure consisting of alternating layers of SiO2 (serving as interlayer insulating layers) and SiN (serving as sacrificial layers) stacked on a substrate W. Furthermore, a plurality of storage trenches 4 extending through the laminate 3 are provided in a direction perpendicular to the surface of the substrate W. Figure 2 (a) is Figure 1 (a) A magnified view of the portion of the stacked body surrounded by A.

[0069] The method for manufacturing the semiconductor device in this embodiment is as follows: Figure 3 As shown, it includes at least a self-assembled monomolecular film (hereinafter referred to as "SAM") formation process S1 and an etching process S2, and selectively etches the SiN layer 2 via the storage trench 4, thereby enabling the formation of a recess on the side of the storage trench 4 in the stack 3. Figure 3 This is a flowchart illustrating an example of the overall process of manufacturing a semiconductor device according to this embodiment.

[0070] <SAM Formation Process>

[0071] SAM formation process S1 is a process in which SAM, serving as a protective layer, is selectively formed on the surface of SiO2 layer 1, which serves as the protected layer. SAM formation process S1 is as follows: Figure 3 As shown, it includes at least: a pretreatment step S101, a surface modification step S102, a first processing solution preparation step S103, a first contact step S104, a second processing solution preparation step S105, and a second contact step S106. Furthermore, the SAM formation step S1 corresponds to the substrate processing method of the present invention.

[0072] 1. Pretreatment process

[0073] The pretreatment step S101 is a process of removing organic molecules that are physically adsorbed onto the surface of the SiO2 layer 1, which serves as the protective layer, and which are coated on the surface of the SiO2 layer 1 in the form of particles or thin films. Although this step is optional, it is preferable to perform this step from the viewpoint of effectively modifying the surface of the substrate W in the surface modification step S102 described later. Specifically, the pretreatment step S101 is performed by bringing a pretreatment liquid into contact with the surface of the substrate W.

[0074] There are no particular limitations on the method of bringing the pretreatment liquid into contact with the substrate W. Examples include: coating the pretreatment liquid onto the surface of the substrate W, spraying the pretreatment liquid onto the surface of the substrate W, or immersing the substrate W in the pretreatment liquid.

[0075] One method for applying a pretreatment liquid to the surface of a substrate W is as follows: The pretreatment liquid is supplied to the central portion of the surface of the substrate W while the substrate W is rotated at a constant speed with its central portion as an axis. As a result, the pretreatment liquid supplied to the surface of the substrate W flows from near the center of the substrate W towards the periphery due to the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire surface of the substrate W. Consequently, the entire surface of the substrate W is covered with the pretreatment liquid, thereby forming a liquid film of the pretreatment liquid.

[0076] There are no particular limitations on the conditions for contacting the pretreatment solution with the substrate W, nor is there a particular limitation on the contact time between the pretreatment solution and the substrate W (the immersion time if the substrate W is immersed in the pretreatment solution for pretreatment), which can be set appropriately. However, by keeping the contact time of the pretreatment solution to less than 1 minute, it is possible to suppress excessive etching of the surface portion of the SiO2 layer. Here, the term "film defect" for SAM in this specification means that the molecules constituting SAM are not directly chemically adsorbed onto the surface of the substrate W (the surface of the SiO2 layer 1 in this embodiment), and that surface is exposed.

[0077] The temperature of the pretreatment solution is not particularly limited and can be set appropriately as needed, such as room temperature. Furthermore, in this specification, "room temperature" means a temperature range of 5°C to 35°C.

[0078] There are no particular limitations on the pretreatment solution; for example, hydrofluoric acid (e.g., HF:deionized water (DIW) = 1:100 by volume) can be used.

[0079] 2. Surface modification process (wet method)

[0080] Surface modification process S102 is, for example, the following process: In such Figure 4 (a) The surface of the SiO2 layer 1 is modified so that the region where the first molecule of SAM is difficult to chemisorb is transformed into a region where the first molecule can chemisorb. In addition, the above-mentioned surface modification process S102 is a process that enables the first molecule to chemisorb at a higher density in the region where the first molecule can chemisorb. Figure 4 (a) is an illustration of the surface state of SiO2 layer 1 before surface modification.

[0081] If surface modification is performed on the surface of SiO2 layer 1 through surface modification process S102, then asFigure 4 (b) is a diagram conceptually showing the surface state of the SiO2 layer 1 after the surface modification. Figure 4 (b) is a diagram conceptually showing the surface state of the SiO2 layer 1 after the surface modification.

[0082] In the present embodiment, the surface modification of the surface of the SiO2 layer 1 is performed by a wet method. More specifically, it is performed by bringing a surface modification liquid into contact with the surface of the substrate W after the pretreatment step S101. As the method of bringing the surface modification liquid into contact with the surface of the substrate W, there is no particular limitation, and for example, a method of applying the surface modification liquid to the surface of the substrate W or a method of spraying the surface modification liquid to the surface of the substrate W, a method of immersing the substrate W in the surface modification liquid, or the like can be exemplified.

[0083] Further, as the method of applying the surface modification liquid to the surface of the substrate W, for example, a method of supplying the surface modification liquid to the central portion of the surface of the substrate W while rotating the substrate W at a constant speed with the central portion as the axis can be exemplified. Thereby, the surface modification liquid supplied to the surface of the substrate W flows from the vicinity of the central portion of the surface of the substrate W to the peripheral portion of the substrate W by the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered with the surface modification liquid, and a liquid film of the surface modification liquid is formed.

[0084] As the surface modification liquid, there is no particular limitation as long as it can impart a hydroxyl group to the surface of the SiO2 layer 1. As the surface modification liquid, specifically, for example, an ammonia hydrogen peroxide mixed solution (Standard Clean-1 (SC-1)) (volumetric ratio, ammonia water (NH3 concentration 28%): hydrogen peroxide water (H2O2 concentration 30%): DIW = 1:4:20), ammonia water, a tetramethylammonium hydroxide aqueous solution, and a trimethyl-2-hydroxyethylammonium hydroxide aqueous solution, and the like alkaline solutions can be exemplified. Among these alkaline solutions, from the viewpoint of imparting a hydroxyl group to the SiO2 layer well, an ammonia hydrogen peroxide mixed solution or the like is preferred.

[0085] As the conditions of bringing the surface modification liquid into contact with the substrate W, there is no particular limitation, and as the time of bringing the surface modification liquid into contact with the substrate W (in the case of performing by immersing the substrate W in the surface modification liquid, the immersion time), there is no particular limitation, and it can be appropriately set. However, by setting the contact time of the surface modification liquid to 10 minutes or more, a hydroxyl group can be sufficiently imparted to the surface of the SiO2 layer 1. Thereby, it is possible to reduce the region where the first molecule cannot be chemisorbed, and to chemisorb the first molecule at a high density to the surface of the SiO2 layer 1. As a result, it is possible to suppress the generation of film defects, and thereby to efficiently form a SAM excellent in density and protection performance in a short time.

[0086] The temperature of the surface modification liquid is not particularly limited and can be appropriately set as needed, for example, at room temperature or the like.

[0087] Further, in the case where the surface modification process S102 is performed by a wet method, a cleaning process for removing the surface modification liquid and a drying process can be sequentially performed after the surface modification process S102 is completed. The cleaning method in the cleaning process is not particularly limited and can be exemplified by a method of supplying a cleaning liquid to the surface of the substrate W or a method of immersing the substrate W in a cleaning liquid, or the like. In addition, the cleaning liquid can be exemplified by toluene, decane, 1,3-bis(trifluoromethyl)benzene, or the like. 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 appropriately set as needed. The purpose of the drying process is to remove the cleaning liquid remaining on the surface of the substrate W. The drying method is not particularly limited and can be exemplified by a method of blowing a non-active gas such as nitrogen to the surface of the substrate W, or the like. The drying conditions such as the drying time and the drying temperature are not particularly limited and can be appropriately set as needed.

[0088] 3. First treatment liquid preparation process

[0089] The first treatment liquid preparation process S103 is a process of preparing a first treatment liquid containing a first molecule or the like. As the first molecule contained in the first treatment liquid, a molecule having a functional group capable of undergoing a dehydration condensation reaction with a hydroxyl group can be exemplified. By causing the first molecule to have the functional group, a dehydration condensation reaction can be induced between the functional group and a hydroxyl group on the surface of the SiO2layer 1 as the protective layer. As a result, the first molecule can be directly chemisorbed to the surface of the SiO2layer 1 as the protective layer to form a SAM. Hereinafter, as the first molecule contained in the first treatment liquid, a case where the functional group capable of undergoing a dehydration condensation reaction with a hydroxyl group is a hydroxyl group will be exemplified.

[0090] First, a dispersion liquid in which water is uniformly dispersed in an organic solvent as a main solvent is prepared. By "water being uniformly dispersed in an organic solvent" is meant that, for example, water is present in the organic solvent in the state of an emulsion. In addition, "main solvent" means the solvent having the largest volume ratio when a mixed solvent containing a plurality of solvents is used.

[0091] As the organic solvent as the main solvent, for example, an ether solvent, an aromatic hydrocarbon-based solvent, an aliphatic hydrocarbon-based solvent, a fluorine-based solvent, a ketone-based solvent, and the like can be exemplified. As the ether solvent, there is no particular limitation, and for example, tetrahydrofuran (THF) and the like can be exemplified. As the aromatic hydrocarbon-based solvent, there is no particular limitation, and for example, toluene and the like can be exemplified. As the aliphatic hydrocarbon-based solvent, there is no particular limitation, and for example, decane and the like can be exemplified. As the fluorine-based solvent, there is no particular limitation, and for example, 1,3-bis(trifluoromethyl)benzene and the like can be exemplified. As the ketone-based solvent, there is no particular limitation, and for example, methyl ethyl ketone and the like can be exemplified. These solvents can be used alone or in combination of two or more. Among the exemplified solvents, from the viewpoint of affinity with water, the aromatic hydrocarbon-based solvent is preferred, and toluene is particularly preferred. In addition, as the organic solvent as the main solvent, a solvent having a low solubility to water is preferred. Thereby, water can be well dispersed in the organic solvent. As the organic solvent having a low solubility to water, for example, toluene and the like described above can be exemplified.

[0092] The amount of water added to the dispersion liquid is preferably in a range of 50 ppm or more and 200 ppm or less, and more preferably in a range of 50 ppm or more and 150 ppm or less. By setting the amount of water added to 50 ppm or more, it is possible to prevent the insufficient introduction of a hydroxyl group (a functional group capable of undergoing a dehydration condensation reaction with a hydroxyl group) to the first molecule in the hydrolysis reaction with the water. That is, in the generation stage of the first treatment liquid, a sufficient amount of the first molecule having a hydroxyl group can exist in the first treatment liquid. As a result, even without contacting the treatment liquid with the substrate surface for a long time in order to form a dense SAM as in the conventional substrate treatment method, it is possible to suppress the generation of film defects and form a SAM excellent in density. On the other hand, by setting the amount of water added to 200 ppm or less, it is possible to suppress the excessive aggregation of the first molecules having a hydroxyl group with each other due to a dehydration condensation reaction. As a result, it is possible to suppress the decrease in the density of the first molecule chemisorbed to the substrate surface, and thereby form a SAM excellent in density.

[0093] As the method for producing the dispersion liquid, there is no particular limitation, and for example, a method in which an organic solvent and water are mixed while applying ultrasonic waves, a method in which an organic solvent and water are mixed and then ultrasonic waves are applied, and the like can be exemplified. 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 application conditions of ultrasonic waves, specifically, for example, the application time, the frequency, the sound wave intensity, and the like are not particularly limited as long as the water is dispersed in the organic solvent to an extent, and can be appropriately set as needed. In addition, the method for applying ultrasonic waves is not particularly limited, and for example, a method in which an ultrasonic wave vibrator is immersed in a mixed liquid and the ultrasonic wave vibrator is vibrated to apply ultrasonic waves can be exemplified.

[0094] In addition, the production of the dispersion liquid is preferably performed, for example, in an atmosphere of an inactive gas such as nitrogen. In the case where the production is performed in an environment in which moisture is present in the atmosphere, the moisture in the atmosphere is dissolved in the mixed liquid (or the dispersion liquid), resulting in a dispersion liquid in which the prescribed amount of moisture cannot be obtained, and thus is not preferable.

[0095] Next, a material capable of forming a SAM (hereinafter, referred to as "SAM-forming material") is added to the produced dispersion liquid, thereby preparing a first treatment liquid containing the first molecule having a hydroxyl group. At the time of adding the SAM-forming material to the dispersion liquid, and after the SAM-forming material is added to the dispersion liquid, it is preferable that no ultrasonic wave is applied. By not applying the ultrasonic wave, the first treatment liquid can be produced in a manner in which the first molecules exist without being aggregated with each other. By producing the first treatment liquid in a manner in which the first molecules exist without being aggregated with each other, the SAM can be formed favorably in the first contact process S104 described later.

[0096] As the SAM-forming material, there is no particular limitation as long as a molecule containing a functional group exhibiting a hydrolysis reactivity, and capable of forming a SAM. In addition, as the SAM-forming material, a material having a high affinity (solubility) to the above-described organic solvent is preferable. The SAM-forming material is specifically, for example, an organosilane compound such as octadecyltrichlorosilane (C 18 H 37 SiCl3), decyltrichlorosilane (C 10 H 21 SiCl3), trichloropropylsilane (C3H7SiCl3), trichloromethylsilane (CH3SiCl3), or the like. The exemplified organosilane compound has a trichlorosilane group as a functional group exhibiting a hydrolysis reactivity.

[0097] The first molecule before being added to the first treatment liquid has a functional group exhibiting a hydrolysis reactivity. Therefore, if the SAM-forming material is added to the dispersion liquid, the functional group and the water molecules uniformly dispersed in and present in the dispersion liquid undergo a hydrolysis reaction. Thereby, the functional group exhibiting a hydrolysis reactivity becomes a functional group capable of undergoing a dehydration condensation reaction with the hydroxyl group. For example, in the case where the first molecule is octadecyltrichlorosilane, a reaction as follows occurs.

[0098] C 18 H 37 SiCl3 + 3H2O → C 18 H 37 Si(OH)3 + 3HCl3

[0099] As a result, a first treatment liquid in which the first molecules into which the hydroxyl groups are introduced are not aggregated can be obtained. Thus, by preparing in advance a liquid containing the first molecules into which the hydroxyl groups are introduced as the first treatment liquid, the hydrolysis reaction which becomes a rate-determining step in the SAM film formation process can be omitted. As a result, compared with the conventional treatment liquid, the SAM can be formed in a short time.

[0100] The addition amount of the SAM-forming material is preferably in a range of 0.05% by mass or more and 5% by mass or less with respect to the total mass of the first treatment liquid.

[0101] In the first treatment liquid, a publicly known additive can also be contained within a range not impairing the effects of the present application. As the additive, there is no particular limitation, and for example, a stabilizer, a surfactant, and the like can be exemplified.

[0102] The preparation of the first treatment liquid is preferably performed in a state of being left still. More specifically, when the SAM-forming material is added to the dispersion liquid, it is not preferable to perform while imparting mechanical force such as stirring and oscillation to the dispersion liquid. In the case where the SAM-forming material is added to the dispersion liquid while imparting mechanical force such as stirring and oscillation to the dispersion liquid, the first molecules can be aggregated with each other. However, by preparing the first treatment liquid by adding the SAM-forming material to the dispersion liquid in a state of being left still, the first molecules can be further inhibited from being aggregated with each other to generate the first treatment liquid.

[0103] The content of water in the first treatment liquid is preferably in a range of 50 ppm or more and 200 ppm or less, and more preferably in a range of 50 ppm or more and 150 ppm or less.

[0104] The first treatment liquid preparation step S103 can be performed, for example, at normal temperature and normal pressure. Furthermore, the "normal pressure" in the present specification means a pressure near the standard state of the atmosphere (standard atmospheric pressure), and the standard state of the atmosphere means an atmospheric pressure condition in which the temperature is near about 25°C and the absolute pressure is near about 101 kPa. In addition, the "normal pressure" also includes a case where the pressure is substantially positive or negative with respect to the standard atmospheric pressure.

[0105] 4. First contact step

[0106] The first contact step S104 is a step of forming a SAM by bringing the first treatment liquid containing the first molecules into contact with the surface of the substrate W.

[0107] As the method of bringing the first treatment liquid into contact with the substrate W, there is no particular limitation, and for example, a method of applying the first treatment liquid to the surface of the substrate W or a method of spraying the first treatment liquid to the surface of the substrate W, a method of immersing the substrate W in the first treatment liquid, and the like can be exemplified.

[0108] One method for applying the first processing liquid to the surface of the substrate W is as follows: the first processing liquid is supplied to the center of the surface of the substrate W while the substrate W is rotating at a constant speed with its center portion as an axis. As a result, the first processing liquid supplied to the surface of the substrate W flows from near the center of the substrate W towards the periphery of the substrate W due to the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire surface of the substrate W. Consequently, the entire surface of the substrate W is covered by the first processing liquid, forming a liquid film of the first processing liquid.

[0109] There are no particular limitations on the conditions for contacting the first processing liquid with the substrate W. However, compared to the case of forming SAM using conventional methods, the first contact step S104 of this embodiment can shorten the contact time of the first processing liquid. Specifically, the time required for the SAM formation step S1 (when the substrate W is immersed in the first processing liquid) can be appropriately set within the range of 1 minute to 1540 minutes, preferably 1 minute to 60 minutes, and more preferably 1 minute to 30 minutes, depending on the type of SAM forming material, its concentration, and the type of solvent.

[0110] Next, regarding the formation process of SAM, we will explain it in more detail using the case where the SAM forming material is octadecyltrichlorosilane as an example. If... Figure 4 As shown in (c), the surface of the substrate W is supplied with a first processing liquid, and in the first processing liquid at the time of supply, a first molecule 5 in which hydroxyl groups are introduced into octadecyltrichlorosilane is dispersed. Figure 4 (c) is an explanatory diagram showing the situation where the first processing liquid is supplied to the surface of SiO2 layer 1.

[0111] Here, hydroxyl groups are introduced onto the surface of SiO2 layer 1 through the aforementioned surface modification process S102. Therefore, the first molecule 5... Figure 5 As shown in (a), a dehydration condensation reaction occurs between the hydroxyl group and the hydroxyl group. More specifically, the hydroxyl group of the first molecule 5 undergoes a dehydration condensation reaction with the hydroxyl group on the surface of SiO2 layer 1, thereby forming a siloxane bond, and thus the first molecule 5 is chemically adsorbed onto the surface of SiO2 layer 1. The first molecule 5 exists in the first treatment solution in a state where mutual aggregation is suppressed. Therefore, the dehydration condensation reaction between the hydroxyl group of the first molecule 5 and the hydroxyl group on the surface of SiO2 layer 1, which is the rate-limiting stage in the film formation process of SAM, can be promoted. In addition, the first molecule 5 can be chemically adsorbed onto the surface of SiO2 layer 1 at a high density. Furthermore, Figure 5 (a) is an explanatory diagram showing the chemical adsorption of the first molecule 5 on the surface of SiO2 layer 1.

[0112] Next, if the first molecules 5 are chemically adsorbed to the surface of the SiO2layer 1 at high density, island structures of the first molecules 5 appear on the surface. Further, in each island, the first molecules 5 self-assemble and grow (expand) by the hydrophobic interaction or the electrostatic interaction with each other, and finally form a SAM 6 (refer to Figure 5 (b)). However, in the SAM 6, at the boundary between the islands adjacent to each other where the first molecules 5 do not enter, or at the region of the surface of the SiO2layer 1 where the first molecules 5 do not chemically adsorb and exist as adhered, film defects 7 are sometimes generated. Figure 5 (b) is an explanatory view showing a case where the first molecules 5 self-assemble on the surface of the SiO2layer 1 to form the SAM 6.

[0113] 5. Second treatment liquid preparation step

[0114] The second treatment liquid preparation step S105 is a step of generating a second treatment liquid containing second molecules. The second molecules contained in the second treatment liquid have a functional group capable of performing a dehydration condensation reaction with a hydroxyl group, and are capable of directly chemically adsorbing to the surface of the SiO2layer 1, thereby reducing or repairing film defects of the SAM.

[0115] The second treatment liquid can be prepared by the same method as the first treatment liquid. In addition, as a material for making the second treatment liquid, the material used in the first treatment liquid can be used without particular limitation.

[0116] Here, as the second molecules contained in the second treatment liquid, the same kind or different kind of molecules as the first molecules can be used. In addition, as the second molecules, molecules having the same or shorter molecular chain length than the first molecules are preferable, and molecules having shorter molecular chain length than the first molecules are more preferable. For example, in the case where the first molecules are C 18 H 37 Si(OH)3, C3H7Si(OH)3, or CH3Si(OH)3, or the like. 10 H 21 Si(OH)3, C3H7Si(OH)3, or CH3Si(OH)3, or the like.

[0117] 6. Second contact step

[0118] The second contact step S106 is a step of bringing the second treatment liquid containing the second molecules into contact with the surface of the substrate W after the first contact step S104, repairing the film defects 7 generated in the SAM 6, and performing densification processing on the SAM 6. The second contact step S106 is performed at least once until the area ratio (%) of the film defects of the SAM formed on the surface of the SiO2layer 1 reaches an arbitrarily set threshold value or less. Here, the area ratio (%) of the film defects of the SAM is defined by the following formula.

[0119] Area ratio of membrane defects (%) = (Total area of ​​regions that become membrane defects within any region of the SAM) / (Area of ​​any region within the SAM) × 100

[0120] The threshold for the area ratio (%) of membrane defects is not particularly limited and can be set arbitrarily. Furthermore, the area ratio (%) of membrane defects can be calculated, for example, as follows: An observation image (AFM image) of any region where SAM6 is formed is acquired using atomic force microscopy (AFM), the observation image is binarized, and then image processing is performed to map the membrane defects 7. Thus, the region of membrane defects 7 in SAM6 is determined, the area of ​​the determined region of membrane defects 7 in SAM6 is calculated, and then the proportion of the observed image area relative to the total area is calculated. Furthermore, in the mapping of membrane defects 7, it is preferable to consider the film thickness of SAM6 when performing image processing to map defects from the surface of SAM6 to a depth not exceeding the film thickness of SAM6.

[0121] Furthermore, when performing multiple second contact steps S106, the second molecule contained in the second treatment liquid can be changed in each step. In this case, the second molecule used in the earlier steps preferably has a molecular chain length that is the same as or longer than that used in the later steps. For example, C is used in the first second contact step. 10 H 21 When Si(OH)3 is used as the second molecule, it is preferable to use a second molecule such as C3H7Si(OH)3 or CH3Si(OH)3 in the second contact step. Each time the second contact step is repeated, the second molecule is chemically adsorbed onto the film defects 7 of SAM6, resulting in a reduction in the area of ​​the film defects 7. Therefore, in subsequent steps, if a second molecule with a shorter molecular chain length is used, the possibility of steric hindrance preventing chemical adsorption onto the surface of the SiO2 layer 1 can be reduced or suppressed, thereby further improving the density.

[0122] The method for contacting the second processing liquid with the substrate W is the same as that described in the first contact process S104. Therefore, its detailed description is omitted. Furthermore, the conditions for contacting the second processing liquid with the substrate W can be appropriately set depending on the type of the second processing liquid, etc.

[0123] When the SAM forming material is octadecyltrichlorosilane, the surface of SAM6 in the second contact step S106 is as follows: Figure 5 As shown in (c). Figure 5 (c) is an explanatory diagram showing the second processing liquid being supplied to the surface of SiO2 layer 1. That is, as... Figure 5(c) shows that if the second treatment liquid is supplied to the surface of the substrate W, the second molecules 8 are dispersed in the second treatment liquid at that time. Figure 5 In (c), the second molecules 8 are exemplified by molecules in which a hydroxyl group is introduced in a trichloropropylsilane. Here, the second molecules 8 have a shorter molecular chain length than the first molecules 5' that constitute the SAM 6. Therefore, even in the region of the SAM 6 in which the film defect 7 is generated, the second molecules 8 do not cause steric hindrance with the first molecules 5' that constitute the SAM 6, and undergo dehydration condensation with the hydroxyl groups on the surface of the SiO2layer 1. As a result, siloxane bonds are formed between the second molecules 8 and the hydroxyl groups, and the second molecules 8 are chemisorbed to the surface of the SiO2layer 1. As a result, the film defect 7 generated in the SAM 6 is repaired as shown in (d), and the SAM 6' having excellent density and protection performance is formed. Furthermore, the second molecules 8 that are chemisorbed to the surface of the SiO2layer 1 are not removed by the second contact process S106, and are present on the surface of the SiO2layer 1. Therefore, the second molecules 8 are present on the surface of the SiO2layer 1 even after the second contact process S106. Figure 6 (d) is an explanatory view showing the state of the SAM 6' after the densification process. Figure 6 (d) is an explanatory view showing the state of the SAM 6' after the densification process.

[0124] 7. Other processes

[0125] The removal process and the drying process can also be performed sequentially after the first contact process S104 and the second contact process S106, respectively. As a result, the first treatment liquid remaining on the surface of the SiO2layer 1 after the first contact process S104 or the second treatment liquid remaining on the surface of the SiO2layer 1 after the second contact process S106 can be removed. As a result, the first molecules 5 or the second molecules 8 that are not useful for forming the SAM 6' can be removed, and more specifically, the first molecules 5 or the second molecules 8 that are not chemisorbed to the surface of the SiO2layer 1 can be removed. As a result, a film containing the unadsorbed first molecules 5 or the second molecules 8 can be prevented from being formed on the SAM 6', and a good monomolecular film can be formed.

[0126] The removal process is a process in which the first treatment liquid or the second treatment liquid (hereinafter, referred to as "the first treatment liquid or the like") remaining on the surface of the SiO2layer 1 is replaced with a removal liquid to be removed. The method of removing the first treatment liquid or the like from the surface of the SiO2layer 1 is not particularly limited, and for example, a method in which the removal liquid is applied to the surface of the substrate W or a method in which the removal liquid is sprayed to the surface of the substrate W, a method in which the substrate W is immersed in the removal liquid, or the like can be exemplified.

[0127] One method for applying a removal liquid to the surface of a substrate W is as follows: the removal liquid is supplied to the center of the surface of the substrate W while the substrate W is rotating at a constant speed with its center portion as an axis. As a result, the removal liquid supplied to the surface of the substrate W is propelled by the centrifugal force generated by the rotation of the substrate W, flowing from near the center of the surface of the substrate W towards the periphery and spreading to the entire surface of the substrate W. Consequently, the first processing liquid or the like on the surface of the substrate W is replaced by the removal liquid, and the entire surface of the substrate W is covered by the removal liquid, thereby forming a liquid film of the removal liquid.

[0128] The removal liquid is not particularly limited, but an organic solvent with low solubility in water and capable of dissolving the SAM forming material is preferred. If the removal liquid can dissolve the SAM forming material, it can effectively remove excess first molecule 5 or second molecule 8 that does not contribute to SAM formation from the surface. More specifically, examples of removal liquids include toluene, decane, and 1,3-bis(trifluoromethyl)benzene. These solvents can be used alone or in mixtures of two or more.

[0129] The purpose of the drying process is to remove the removal liquid remaining on the surface of the substrate W. There are no particular limitations on the drying method; for example, blowing an inactive gas such as nitrogen onto the surface of the substrate W is acceptable. Drying conditions such as drying time and temperature are not particularly limited as long as the removal liquid is removed to a certain extent, and can be set appropriately as needed.

[0130] Based on the above, in the SAM forming process S1, as follows: Figure 6 As shown, a SAM6' with excellent density and protective properties can be formed on the surface of the SiO2 layer 1. In this embodiment, after hydroxyl groups are pre-introduced onto the surface of the SiO2 layer 1 in the surface modification step S102, SAM6 is formed in the first contact step S104. Furthermore, a densification treatment of SAM6 is performed in the second contact step S106, thereby repairing the film defects 7 generated in the SAM6. As a result, even without prolonged contact of the treatment solution with the surface of the SiO2 layer 1 to form a dense film, the generation of film defects can be suppressed, thereby efficiently forming a SAM6' with excellent density and protective properties in a short time.

[0131] Furthermore, in this embodiment, immediately after the drying process, a rinsing process and other drying processes can be performed. The rinsing process removes the removal liquid from the surface of the SiO2 layer 1. Additionally, other drying processes remove the rinsing liquid used in the rinsing process.

[0132] As the rinsing liquid in the rinsing process, there is no particular limitation, and for example, DIW or the like can be exemplified. As a method of supplying the rinsing liquid to the surface of the substrate W, there is no particular limitation, and for example, a method of applying the rinsing liquid to the surface of the substrate W or a method of spraying the rinsing liquid to the surface of the substrate W, a method of immersing the substrate W in the rinsing liquid, or the like can be exemplified.

[0133] As the method of applying the rinsing liquid to the surface of the substrate W, for example, a method of supplying the rinsing liquid to the central portion of the surface of the substrate W while rotating the substrate W at a constant speed with the central portion as a shaft can be exemplified. Thereby, the rinsing liquid supplied to the surface of the substrate W flows from the vicinity of the center of the surface of the substrate W to the peripheral portion of the substrate W by the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire surface of the substrate W. As a result, the removal liquid on the surface of the substrate W is replaced with the rinsing liquid, and the entire surface of the substrate W is covered with the rinsing liquid, thereby forming a liquid film of the rinsing liquid.

[0134] The other drying process aims at removing the rinsing liquid remaining on the surface of the substrate W. As the drying method, there is no particular limitation, and for example, a method of blowing a non-active gas such as nitrogen to the surface of the substrate W or the like can be exemplified. The drying conditions such as the drying time and the drying temperature are not particularly limited as long as the rinsing liquid is removed to an extent, and can be appropriately set as necessary.

[0135] < Etching Process (Monolithic) >

[0136] The etching process S2 is a process of selectively etching the SiN layer 2 which is a sacrifice layer and an etching layer. More specifically, it is a process of removing the SiN layer 2 by bringing the etching liquid into contact with the SiN layer 2 via the storage trench 4. In this process, the SAM 6' functions as a protective layer to protect the SiO2 layer 1. Thereby, the SiO2 layer 1 can be favorably inhibited from being etched.

[0137] As the method of applying the etching liquid to the surface of the substrate W, for example, a method of supplying the etching liquid to the central portion of the surface of the substrate W while rotating the substrate W at a constant speed with the central portion as a shaft can be exemplified in the case of performing by the monolithic method. Thereby, the etching liquid supplied to the surface of the substrate W flows from the vicinity of the center of the surface of the substrate W to the peripheral portion of the substrate W by the centrifugal force generated by the rotation of the substrate W, and diffuses to the entire surface of the substrate W. As a result, the entire surface of the substrate W is covered with the etching liquid, thereby forming a liquid film of the etching liquid.

[0138] The etching solution can be appropriately set considering factors such as the constituent material of the layer being etched or the etching rate. In the case where the layer being etched is SiN layer 2, as shown in this embodiment, an aqueous solution of phosphoric acid (H3PO4) or hydrofluoric acid (e.g., HF:DIW = 1:100 by volume) can be used as the etching solution. Furthermore, the concentration of the etching solution can also be appropriately set considering factors such as the constituent material of the layer being etched or the etching rate.

[0139] In addition, the etching temperature (i.e., the temperature of the etching solution) and the etching rate of the etched layer can be appropriately set by taking into account the constituent material of the etched layer.

[0140] Furthermore, immediately after the etching process S2 is completed, a rinsing process for removing the etching solution and a drying process are preferably performed sequentially. The rinsing method in the rinsing process is not particularly limited; examples include supplying rinsing solution to the surface of the substrate W or immersing the substrate W in the rinsing solution. The rinsing solution is not particularly limited; examples include DIW. Furthermore, the rinsing time and the temperature of the rinsing solution are not particularly limited and can be set appropriately as needed. The purpose of the drying process is to remove the rinsing solution remaining on the surface of the substrate W. The drying method is not particularly limited; examples include blowing an inactive gas such as nitrogen onto the surface of the substrate W. The drying time and the drying temperature are not particularly limited and can be set appropriately as needed.

[0141] Based on the above, in etching process S2, it can be done as follows: Figure 2 As shown in (c), only the SiN layer 2 is selectively removed. Furthermore, in the SiO2 layer 1, since SAM6', with its excellent density and protective properties, is coated on its surface for protection, it is possible to prevent the SiO2 layer 1 from being etched, or for etched silicon components to precipitate and adhere to the surface of the SiO2 layer 1. Furthermore, it is also possible to increase the permissible range of silicon concentration contained in the etching solution such as phosphoric acid. In addition, Figure 2 (c) is Figure 1 (b) is a magnified view of the portion surrounded by B in the stack, showing the state of SiN layer 2 after etching.

[0142] [Substrate processing apparatus (semiconductor manufacturing apparatus)]

[0143] Next, the substrate processing apparatus of this embodiment will be described below, taking the case of a semiconductor manufacturing apparatus as an example.

[0144] The semiconductor manufacturing apparatus 100 in this embodiment is a monolithic processing unit for forming SAM and etching the etched layer, such as Figure 7As shown, there are provided: a substrate holding section 110 that holds a substrate W; a pretreatment liquid supply section 120 that supplies a pretreatment liquid to a surface Wf of the substrate W; a surface modification liquid supply section (surface modification section) 130 that supplies a surface modification liquid to the surface Wf of the substrate W; a first treatment liquid supply section 140 that supplies a first treatment liquid to the surface Wf of the substrate W; an ultrasonic wave application section; a second treatment liquid supply section 150 that supplies a second treatment liquid; a non-reactive gas supply section (not shown) that supplies a non-reactive gas; an etching liquid supply section (etching section) 160; a chamber 170 that is a container that houses the substrate W; a flying particle prevention cover 180 that traps treatment liquids; a rotation drive section 190 that independently drives arms described later of each section to rotate; and a control section 300. In addition, the semiconductor manufacturing apparatus 100 can also be provided with a load / unload mechanism (not shown) that loads or unloads the substrate W. Further, Figure 7 is an explanatory diagram showing the schematic structure of the semiconductor manufacturing apparatus 100 of the present embodiment. In Figure 7 , in order to clearly show the directional relationship of the structure, XYZ orthogonal coordinate axes are appropriately shown. Here, the XY plane represents a horizontal plane, and the +Z direction represents a vertical upward direction.

[0145] <Substrate holding section>

[0146] The substrate holding section 110 is a mechanism that holds the substrate W, as shown in Figure 7 , is a mechanism that holds the substrate W in a substantially horizontal posture with the surface Wf of the substrate W facing upward and rotates the substrate W. The substrate holding section 110 has a rotation chuck 113 that is integrally combined with a rotation base 111 and a rotation shaft 112. The rotation base 111 has a substantially circular shape in plan view, and a hollow rotation shaft 112 that extends in a substantially vertical direction is fixed to the center portion thereof. The rotation shaft 112 is connected to a rotation shaft of a chuck rotation mechanism 114 that includes a motor. The chuck rotation mechanism 114 is housed in a cylindrical housing 115, and the rotation shaft 112 is supported by the housing 115 so as to be freely rotatable about a rotation axis J1 in the vertical direction.

[0147] The chuck rotation mechanism 114 is capable of rotating the rotation shaft 112 about the rotation axis J1 by driving from a chuck drive section (not shown) of the control section 300. Thereby, the rotation base 111 mounted to the upper end portion of the rotation shaft 112 is rotated about the rotation axis J1 at a constant speed. The control section 300 is capable of controlling the chuck rotation mechanism 114 via the chuck drive section, thereby adjusting the rotation speed of the rotation base 111.

[0148] A plurality of chuck pins 116 are erected near the periphery of the rotating base 111 to hold the peripheral end of the substrate W. While the number of chuck pins 116 is not particularly limited, it is preferable to provide at least three to reliably hold the circular substrate W. In this embodiment, three chuck pins are arranged at equal intervals along the periphery of the rotating base 111. Each chuck pin 116 includes: a substrate support pin that supports the periphery of the substrate W from below; and a substrate holding pin that presses against the outer peripheral end face of the substrate W supported by the substrate support pin to hold the substrate W.

[0149] <Pretreatment Liquid Supply Department>

[0150] The pretreatment liquid supply unit 120 in this embodiment is a mechanism for supplying pretreatment liquid to the surface Wf of the substrate W. This pretreatment liquid supply unit 120 is as follows: Figure 7 As shown, it has a pretreatment liquid storage section 121, a nozzle 122, and an arm 123.

[0151] Pretreatment liquid storage section 121 Figure 8 As shown, it includes a pressurization unit 124 and a pretreatment liquid tank 125. Furthermore, Figure 8 This is an explanatory diagram showing the schematic structure of the pretreatment liquid storage unit 121 in the pretreatment liquid supply unit 120.

[0152] The pressurization unit 124 includes: a nitrogen supply source 124a that serves as a supply source for pressurizing the gas in the pretreatment liquid tank 125, a pump (not shown) for pressurizing nitrogen, a nitrogen supply pipe 124b, and a valve 124c provided in the path of the nitrogen supply pipe 124b.

[0153] Nitrogen supply pipe 124b is connected to the pretreatment liquid tank 125. Additionally, valve 124c is electrically connected to the control unit 300, and its opening and closing can be controlled by the operation command of the control unit 300. If valve 124c is opened by the operation command of the control unit 300, nitrogen can be supplied to the pretreatment liquid tank 125.

[0154] The pretreatment liquid tank 125 also includes a stirring unit for agitating the pretreatment liquid within the tank 125, and a temperature adjustment unit for adjusting the temperature of the pretreatment liquid (neither shown). The stirring unit can be exemplified by a rotating unit for agitating the pretreatment liquid, and a stirring control unit for controlling the rotation of the rotating unit. The stirring control unit is electrically connected to the control unit 300, and the rotating unit, for example, has a propeller-shaped stirring blade at the lower end of its rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby causing the rotating unit to rotate, thus agitating the pretreatment liquid using the stirring blade. As a result, the concentration and temperature of the pretreatment liquid within the pretreatment liquid tank 125 can be made uniform.

[0155] Further, a discharge pipe 125a for supplying the pretreatment liquid to the nozzle 122 is connected to the pretreatment liquid tank 125. An discharge valve 125b is provided on the midway path of the discharge pipe 125a. In addition, the discharge valve 125b is electrically connected to the control section 300. Thus, the opening and closing of these valves can be controlled by the operation command of the control section 300. If the discharge valve 125b is opened by the operation command of the control section 300, the pretreatment liquid is pressure-fed to the nozzle 122 via the discharge pipe 125a.

[0156] The nozzle 122 is installed at the top end of the arm 123 which is horizontally extended and disposed above the rotary base 111 when the pretreatment liquid is ejected. The arm 123 is connected to the rotation drive section 190 via a rotation shaft (not shown). The rotation drive section 190 is electrically connected to the control section 300 and rotates the arm 123 by the operation command from the control section 300. The nozzle 122 is moved in conjunction with the rotation of the arm 123.

[0157] <Surface Modification Liquid Supply Section (Surface Modification Section)>

[0158] The surface modification liquid supply section 130 of the present embodiment is a mechanism for supplying a surface modification liquid to the surface Wf of the substrate W. As shown in FIG. 1, the surface modification liquid supply section 130 has a surface modification liquid storage section 131, a nozzle 132, and an arm 133. Figure 7

[0159] The surface modification liquid storage section 131 has a function of supplying the surface modification liquid to the nozzle 132 as shown in FIG. 2 and is provided with a pressurizing section 134 and a surface modification liquid tank 135. Figure 9 Figure 9 is an explanatory view showing the schematic structure of the surface modification liquid storage section 131 in the surface modification liquid supply section 130.

[0160] The pressurizing section 134 is provided with a nitrogen gas supply source 134a which is a supply source of a gas 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 on the midway path of the nitrogen gas supply pipe 134b.

[0161] 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 section 300 and the opening and closing of the valve 134c can be controlled by the operation command of the control section 300. If the valve 134c is opened by the operation command of the control section 300, the nitrogen gas can be supplied to the surface modification liquid tank 135.

[0162] ​​The surface modification liquid tank 135 may also include a stirring unit for stirring the surface modification liquid within the tank 135, and a temperature adjustment unit for adjusting the temperature of the surface modification liquid (neither shown). As the stirring unit, examples include a rotating unit for stirring the surface modification liquid within the tank 135, and a stirring control unit for controlling the rotation of the rotating unit. The stirring control unit is electrically connected to the control unit 300, and the rotating unit, for example, has a propeller-shaped stirring blade at the lower end of its rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby causing the rotating unit to rotate, thus enabling the stirring blade to stir the surface modification liquid. As a result, the concentration and temperature of the surface modification liquid within the surface modification liquid tank 135 can be made uniform.

[0163] Furthermore, a discharge pipe 135a for supplying the surface-modifying liquid to the nozzle 132 is connected to the surface-modifying liquid tank 135. A discharge valve 135b is provided in the middle of the path of the discharge pipe 135a. The discharge valve 135b is electrically connected to the control unit 300. Thus, the opening and closing of the discharge valve 135b can be controlled by the operation command of the control unit 300. If the discharge valve 135b is opened by the operation command of the control unit 300, the surface-modifying liquid is pressurized to the nozzle 132 through the discharge pipe 135a.

[0164] Nozzle 132 is mounted on the top end of horizontally extending arm 133 and positioned above rotating base 111 when spraying surface-modifying liquid. Arm 133 is connected to rotary drive unit 190 via a rotary shaft (not shown). Rotary drive unit 190 is electrically connected to control unit 300 and rotates arm 133 via operation commands from control unit 300. As arm 133 rotates, nozzle 132 also moves.

[0165] <First Processing Fluid Supply Department>

[0166] The first processing liquid supply unit 140 in this embodiment is a mechanism for supplying a first processing liquid to the surface Wf of the substrate W. This first processing liquid supply unit 140 is as follows: Figure 7 As shown, it has a first processing liquid storage section 141, a first nozzle 142, and a first arm 143.

[0167] First processing liquid storage section 141 Figure 10 As shown, it includes: a first organic solvent supply unit 144, a first water supply unit 145, a first SAM forming material supply unit 146, a first processing liquid tank 147, a first temperature adjustment unit 148, and a first inactive gas supply unit 149. Furthermore, Figure 10 This is an explanatory diagram showing the schematic structure of the first processing liquid storage unit 141 and the ultrasonic application unit 191 in the first processing liquid supply unit 140.

[0168] The first organic solvent supply section 144 includes a first organic solvent storage section 144a that stores an organic solvent, a first organic solvent supply pipe 144b that supplies the organic solvent to the first treatment liquid tank 147, and a first valve 144c provided midway in the path of the first organic solvent supply pipe 144b. The first valve 144c is electrically connected to the control section 300. Thus, the opening and closing of the first valve 144c can be controlled by an operation command from the control section 300. If the first valve 144c is opened by an operation command from the control section 300, the organic solvent is supplied to the first treatment liquid tank 147 via the first organic solvent supply pipe 144b. Furthermore, the organic solvent in the first organic solvent storage section 144a is sent to the first organic solvent supply pipe 144b by a pressurizing mechanism not shown. There is no particular limitation on the pressurizing mechanism, and a known mechanism using a pump or the like can be used.

[0169] The first water supply section 145 includes a first water storage section 145a that stores water, a first water supply pipe 145b that supplies water to the first treatment liquid tank 147, and a first valve 145c provided midway in the path of the first water supply pipe 145b. The first valve 145c is electrically connected to the control section 300. Thus, the opening and closing of the first valve 145c can be controlled by an operation command from the control section 300. If the first valve 145c is opened by an operation command from the control section 300, water is supplied to the first treatment liquid tank 147 via the first water supply pipe 145b. Furthermore, the water in the first water storage section 145a is sent to the first water supply pipe 145b by a pressurizing mechanism not shown. There is no particular limitation on the pressurizing mechanism, and a known mechanism using a pump or the like can be used.

[0170] The first SAM-forming material supply section 146 includes a first SAM-forming material storage section 146a that stores a SAM-forming material, a first SAM-forming material supply pipe 146b that supplies the SAM-forming material to the first treatment liquid tank 147, and a first valve 146c provided midway in the path of the first SAM-forming material supply pipe 146b. The first valve 146c is electrically connected to the control section 300. Thus, the opening and closing of the first valve 146c can be controlled by an operation command from the control section 300. If the first valve 146c is opened by an operation command from the control section 300, the SAM-forming material is supplied to the first treatment liquid tank 147 via the first SAM-forming material supply pipe 146b. Furthermore, the SAM-forming material in the first SAM-forming material storage section 146a is sent to the first SAM-forming material supply pipe 146b by a pressurizing mechanism not shown. There is no particular limitation on the pressurizing mechanism, and a known mechanism using a pump or the like can be used.

[0171] The first treatment liquid tank 147 mixes the organic solvent supplied from the first organic solvent supply section 144 with the water supplied from the first water supply section 145, and the ultrasonic wave application section 191 applies ultrasonic waves to the obtained mixed liquid, thereby generating a dispersion liquid in which water is uniformly dispersed in the organic solvent. In addition, the dispersion liquid can also be generated by mixing the organic solvent supplied from the first organic solvent supply section 144 with the water supplied from the first water supply section 145 while applying ultrasonic waves from the ultrasonic wave application section 191. Further, by supplying the SAM forming material from the first SAM forming material supply section 146 in a state in which the generated dispersion liquid is stored, a treatment liquid can be generated.

[0172] The first treatment liquid tank 147 can also be provided with a first temperature adjustment section 148 for temperature adjustment of the dispersion liquid or the first treatment liquid stored in the inside. The first temperature adjustment section 148 is electrically connected to the control section 300. The control section 300 issues an operation instruction to the first temperature adjustment section 148, thereby being able to control the liquid temperature of the dispersion liquid at the time of generation of the dispersion liquid. Thereby, it is possible to prevent the water in the dispersion liquid from being vaporized (evaporated), and thus the composition of the dispersion liquid from changing.

[0173] The first non-active gas supply section 149 is provided with a first non-active gas supply source 149a as a supply source for supplying non-active gas into the first treatment liquid tank 147, a pump (not shown) for pressurizing the non-active gas, a first non-active gas supply pipe 149b, and a first valve 149c provided midway in the path of the first non-active gas supply pipe 149b.

[0174] The first non-active gas supply pipe 149b is connected to the first treatment liquid tank 147. The first valve 149c is electrically connected to the control section 300, and the opening and closing of the first valve 149c can be controlled by the operation instruction of the control section 300. If the valve is opened by the operation instruction of the control section 300, non-active gas can be supplied to the first treatment liquid tank 147. Thereby, the generation of the dispersion liquid and the first treatment liquid can be performed in an atmosphere of non-active gas. In addition, there is no particular limitation on the non-active gas, and for example, nitrogen gas or the like can be exemplified.

[0175] Further, a first discharge pipe 147a for supplying the first treatment liquid to the first nozzle 142 is connected to the first treatment liquid tank 147. A first discharge valve 147b is provided on the midway path of the first discharge pipe 147a. In addition, the first discharge valve 147b is electrically connected to the control section 300. Thus, the opening and closing of the first discharge valve 147b can be controlled by the operation command of the control section 300. If the first discharge valve 147b and the first valve 149c are opened and the first valves 144c, 145c and 146c are closed by the operation command of the control section 300, the first treatment liquid is pressurized and fed to the first nozzle 142 via the first discharge pipe 147a.

[0176] The first nozzle 142 is mounted to the top end portion of the first arm 143 which is horizontally extended and disposed above the rotary base 111 when the first treatment liquid is ejected. The first arm 143 is connected to the rotation drive section 190 via a rotation shaft (not shown). The rotation drive section 190 is electrically connected to the control section 300 and rotates the first arm 143 by the operation command from the control section 300. The first nozzle 142 is moved in conjunction with the rotation of the first arm 143.

[0177] <Second treatment liquid supply section>

[0178] The second treatment liquid supply section 150 of the present embodiment is a mechanism for supplying the second treatment liquid to the surface Wf of the substrate W. As shown in FIG. 1, the second treatment liquid supply section 150 has a second treatment liquid storage section 151, a second nozzle 152, and a second arm 153. Figure 7

[0179] The same structure as the first treatment liquid storage section 141 shown in FIG. 1 can be employed as the second treatment liquid storage section 151. Therefore, the detailed description thereof is omitted. Figure 10

[0180] The second nozzle 152 is mounted to the top end portion of the second arm 153 which is horizontally extended and disposed above the rotary base 111 when the second treatment liquid is ejected. The second arm 153 is connected to the rotation drive section 190 via a rotation shaft (not shown). The rotation drive section 190 is electrically connected to the control section 300 and rotates the second arm 153 by the operation command from the control section 300. The second nozzle 152 is moved in conjunction with the rotation of the second arm 153.

[0181] <Supersonic wave application section>

[0182] The supersonic wave application section 191 is a mechanism for applying the supersonic wave to the surface Wf of the substrate W. As shown in FIG. 1, the supersonic wave application section 191 has a supersonic wave generator 192 and a supersonic wave horn 193. Figure 10 ​​As shown, in the first treatment liquid tank 147 of the first treatment liquid supply section 140, a mechanism that applies ultrasonic waves at the time of generating a dispersion liquid. Also, the ultrasonic wave application section 191 is a mechanism that applies ultrasonic waves at the time of generating a dispersion liquid in the second treatment liquid tank of the second treatment liquid supply section 150. The ultrasonic wave application section 191 is electrically connected to the control section 300, and can control the application of ultrasonic waves by an operation command of the control section 300.

[0183] The ultrasonic wave application section 191 has, for example, at least an ultrasonic wave vibrator provided in the first treatment liquid tank 147 (in the second treatment liquid tank in the second treatment liquid storage section 151), and an oscillator that applies a drive voltage to the ultrasonic wave vibrator (neither is shown). As the ultrasonic wave vibrator, one that has a piezoelectric body such as a piezoelectric ceramic, and a pair of electrodes provided to the piezoelectric body can be exemplified. The pair of electrodes is in contact with the piezoelectric body, and is also electrically connected to the oscillator. If the oscillator outputs, for example, a high frequency voltage as a drive voltage to the ultrasonic wave vibrator according to an operation command of the control section 300, and applies the drive voltage between the pair of electrodes, the drive voltage is applied to the piezoelectric body. The piezoelectric body to which the drive voltage is applied repeatedly contracts and expands alternately according to the drive voltage from the oscillator, thereby generating vibrations. Thus, it is possible to apply ultrasonic waves to a mixed liquid of water and an organic solvent stored in the first treatment liquid tank 147 or the second treatment liquid tank.

[0184] <Removal liquid supply section>

[0185] The removal liquid supply section of the present embodiment is a mechanism that supplies a removal liquid to the surface Wf of the substrate W. The removal liquid supply section has a removal liquid storage section, a nozzle, and an arm (none of which is shown).

[0186] The removal liquid storage section has a function of supplying a removal liquid to the nozzle, and has a pressurizing section and a removal liquid tank.

[0187] The pressurizing section has a nitrogen gas supply source that is a supply source of a gas that pressurizes the inside of the removal liquid tank, a pump that pressurizes the nitrogen gas, a nitrogen gas supply pipe, and a valve provided in the middle of the path of the nitrogen gas supply pipe.

[0188] The nitrogen gas supply pipe is connected to the removal liquid tank. Also, the valve is electrically connected to the control section 300, and can control the opening and closing of the valve by an operation command of the control section 300. If the valve is opened by the operation command of the control section 300, the nitrogen gas can be supplied to the removal liquid tank.

[0189] The removal liquid tank can also have a stirring unit that stirs the removal liquid in the removal liquid tank, and a temperature adjustment unit that adjusts the temperature of the removal liquid (neither shown). As the stirring unit, there can be a rotating unit that stirs the removal liquid in the removal liquid tank, and a stirring control unit that controls the rotation of the rotating unit. The stirring control unit is electrically connected to the control unit 300, and the rotating unit has, for example, a propeller-shaped stirring blade at the lower end of a rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby causing the rotating unit to rotate, and thereby enabling the stirring blade to stir the removal liquid. As a result, the concentration and temperature of the removal liquid can be made uniform in the removal liquid tank.

[0190] Further, a discharge pipe for supplying the removal liquid to the nozzle is connected to the removal liquid tank. A discharge valve is provided on the midway path of the discharge pipe. The discharge valve is electrically connected to the control unit 300. Thus, the opening and closing of the discharge valve can be controlled by the operation command of the control unit 300. If the discharge valve is opened by the operation command of the control unit 300, the removal liquid is pressurized and fed to the nozzle via the discharge pipe.

[0191] The nozzle is attached to the tip end of an arm that is horizontally extended and disposed above the rotary base 111 when the removal liquid is sprayed. 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 causes the arm to rotate by the operation command from the control unit 300. The nozzle also moves in conjunction with the rotation of the arm.

[0192] <Non-active gas supply unit>

[0193] The non-active gas supply unit is a mechanism that supplies a non-active gas to the surface Wf of the substrate W. The non-active gas supply unit has a non-active gas storage unit, a nozzle, and an arm (none of which are shown).

[0194] The non-active gas storage unit has a function of supplying a non-active gas to the nozzle, and has a non-active gas tank that stores the non-active gas, a non-active gas temperature adjustment unit that adjusts the temperature of the non-active gas stored in the non-active gas tank, and a pipe. As the non-active gas stored in the non-active gas tank, for example, nitrogen gas or the like can be exemplified.

[0195] The non-active gas temperature adjustment unit is electrically connected to the control unit 300, and adjusts the temperature by heating or cooling the non-active gas stored in the non-active gas tank by the operation command of the control unit 300. As the non-active gas temperature adjustment unit, there is no particular limitation, and for example, a known temperature adjustment mechanism such as a Peltier element, a pipe through which temperature-adjusted water flows, or the like can be used.

[0196] The inactive gas storage unit is connected to the nozzle pipeline via piping, and a valve is inserted along the path of the piping. The inactive gas in the inactive gas tank is pressurized and sent to the piping by a pressurizing mechanism (not shown). In addition, the pressurizing mechanism can be implemented by compressing the inactive gas and storing it in the inactive gas tank, in addition to pressurizing by a pump or the like.

[0197] The valve is electrically connected to the control unit 300 and is normally in the closed state. The valve is opened or closed by an operation command from the control unit 300. If the valve is opened by an operation command from the control unit 300, inactive gas is supplied from the nozzle to the surface Wf of the substrate W via a piping.

[0198] The nozzle is mounted at the top of a horizontally extending arm and positioned above the rotating base 111 when discharging inactive gases. The arm is connected to a rotary drive unit 190 via a rotary shaft (not shown). The rotary drive unit 190 is electrically connected to a control unit 300, and the arm rotates via an operation command from the control unit 300. The nozzle moves along with the rotation of the arm.

[0199] <Etching Solution Supply Department (Etching Department)>

[0200] The etching solution supply unit 160 is a mechanism for supplying etching solution to the surface Wf of the substrate W. This etching solution supply unit 160 is as follows: Figure 7 As shown, it has an etching solution storage section 161, a nozzle 162, and an arm 163.

[0201] Etching solution storage section 161 Figure 11 As shown, it includes at least: an etching solution tank 164, a temperature regulator 165, a liquid delivery pump 166, and a particulate filter 167. Furthermore, Figure 11 This is an explanatory diagram showing the schematic structure of the etching solution storage section 161 in the etching solution supply section 160.

[0202] The etching solution tank 164 may also include a stirring unit (not shown) for agitating the etching solution within the tank. Examples of the stirring unit include a rotating part for agitating the etching solution and a stirring control unit for controlling the rotation of the rotating part. The stirring control unit is electrically connected to the control unit 300, and the rotating part has, for example, propeller-shaped stirring blades at the lower end of its rotating shaft. The control unit 300 issues an operation command to the stirring control unit, thereby causing the rotating part to rotate and agitating the etching solution using the stirring blades. As a result, the concentration and temperature of the etching solution can be made uniform within the etching solution tank 164.

[0203] A mixer 168 is provided in the etching solution tank 164. The mixer 168 is capable of mixing a reagent and DIW from a supply source outside not shown and preparing an etching solution at a prescribed concentration. The reagent is a solute that functions as an etchant. As the reagent, phosphoric acid or hydrogen fluoride described above or the like can be exemplified.

[0204] In addition, a discharge pipe 169 for supplying the etching solution to the nozzle 162 is connected to the etching solution tank 164. A temperature adjuster 165, a liquid feeding pump 166, and a particle filter 167 are sequentially inserted in the discharge pipe 169 from the upstream to the downstream in the midway. The temperature adjuster 165 and the liquid feeding pump 166 are electrically connected to the control section 300. Thus, the temperature of the etching solution supplied to the nozzle 162 can be controlled by an operation command of the control section 300. In addition, the etching solution can be fed to the nozzle 162 through the discharge pipe 169 by controlling the liquid feeding pump 166 by the operation command of the control section 300. The particle filter 167 can remove foreign matters such as particles in the etching solution.

[0205] The nozzle 162 is installed at the tip end of the horizontally extending arm 163 and is disposed above the rotary base 111 when the etching solution is ejected. The arm 163 is connected to a rotary drive section 190 via a rotary shaft (not shown). The rotary drive section 190 is electrically connected to the control section 300 and rotates the arm 163 by an operation command from the control section 300. The nozzle 162 is moved in conjunction with the rotation of the arm 163.

[0206] <Anti-spraying cover>

[0207] The anti-spraying cover 180 is provided so as to surround the rotary base 111. The anti-spraying cover 180 is connected to a lift drive mechanism (not shown) and is capable of lifting up and down. When the processing liquid or the like is supplied to the surface Wf of the substrate W, the anti-spraying cover 180 is positioned at a prescribed position by the lift drive mechanism and surrounds the substrate W held by the chuck pin 116 from the side. Thus, the processing liquid or the like that is scattered from the substrate W or the rotary base 111 can be captured.

[0208] <Control section>

[0209] The control unit 300 is electrically connected to each part of the semiconductor manufacturing apparatus to control the operation of each part. The control unit 300 is configured as a computer having an arithmetic unit and a storage unit. As the arithmetic unit, a CPU (Central Processing Unit) is used to perform various arithmetic operations. In addition, the storage unit has a read-only memory (ROM) for storing basic programs, a read-write memory (RAM) for storing various information, and a disk for storing control software and data. The disk pre-stores the generation (mixing) conditions of the dispersion and processing liquid; the supply conditions of the pretreatment liquid, surface modification liquid, first processing liquid, second processing liquid, removal liquid, inactive gas and etching liquid; the application conditions of ultrasonic waves; rinsing conditions; drying conditions; processing conditions of the first contact process and the second contact process; and processing conditions including etching conditions, etc. The CPU reads the processing conditions into the RAM and controls each part of the semiconductor manufacturing apparatus according to its contents.

[0210] (Second Implementation)

[0211] The second embodiment of the present invention will be described below.

[0212] This embodiment differs from the first embodiment in that it utilizes a dry method based on ultraviolet irradiation for the surface modification process. It also differs in that it performs the etching process in batches instead of a single wafer. With this configuration, it is possible to form SAM with high film density and excellent compactness on the substrate surface more efficiently and quickly than conventional film deposition methods, effectively suppressing or reducing film defects and providing excellent protection.

[0213] [Substrate processing method (method for manufacturing semiconductor devices)]

[0214] The substrate processing method (semiconductor device manufacturing method) of this embodiment will be described below. Figure 12 This is a flowchart illustrating an example of the overall process of the substrate processing method according to the second embodiment of the present invention.

[0215] <SAM Formation Process>

[0216] exist Figure 12 In the SAM formation process S1' shown, the pretreatment process S101, the first processing liquid preparation process S103, the first contact process S104, the second processing liquid preparation process S105, and the second contact process S106 are the same as in the first embodiment. Therefore, details of these processes are omitted.

[0217] 1. Surface modification process (dry method)

[0218] The surface modification process S102' is, like the surface modification process S102 of the first embodiment, a process of modifying the surface of the region where the SAM molecules are difficult to chemically adsorb to the region where the SAM molecules can chemically adsorb on the surface of the SiO2layer 1. In addition, the surface modification process S102' is a process of modifying the surface to the region where the SAM molecules can chemically adsorb at a high density.

[0219] In the present embodiment, the surface modification of the surface of the SiO2layer 1 is performed by a dry method based on ultraviolet irradiation. In the case of ultraviolet irradiation, the wavelength of the light source, the irradiation intensity, and the irradiation time, and the like, the irradiation conditions of the ultraviolet light are not particularly limited, as long as it is to the extent that the hydroxyl group can be introduced to the surface of the SiO2layer 1 to the extent that the first molecule 5 or the second molecule 8 can chemically adsorb. In addition, the ultraviolet irradiation is performed, for example, in an atmosphere containing oxygen atoms such as air.

[0220] <etching process (batch type)>

[0221] The etching process S2' is a process of selectively etching the SiN layer 2 of the etched layer by immersing the substrate W after the SAM formation in an etching liquid.

[0222] As a method of immersing the substrate W in the etching liquid, for example, it is performed in a state where the substrate W is in a standing posture. Here, the "standing posture" means a posture of the state where the surface of the substrate W is in a substantially vertical direction with respect to the horizontal plane, and also includes the case of a vertical posture. As the etching liquid, the same etching liquid as described in the first embodiment can be used. In addition, regarding the etching temperature (i.e., the liquid temperature of the etching liquid), and the etching rate for the etched layer, it can also be appropriately set in consideration of the constituent material of the etched layer, as in the case of the first embodiment.

[0223] [substrate processing apparatus (semiconductor manufacturing apparatus)]

[0224] Next, the case where the substrate processing apparatus of the present embodiment is applied to a semiconductor manufacturing apparatus will be described below.

[0225] The semiconductor manufacturing apparatus of the present embodiment differs from the substrate processing apparatus of the first embodiment in that it at least has a single-wafer type substrate processing unit for forming a SAM, and a batch type etching processing unit for etching an etched layer.

[0226] <substrate processing unit>

[0227] As Figure 13As shown, the substrate processing unit 200 of the present embodiment differs from the semiconductor manufacturing apparatus 100 of the first embodiment in that the ultraviolet irradiation section 210 is provided as the surface modification section instead of the surface modification liquid supply section. Figure 13 is an explanatory view showing the schematic structure of the substrate processing unit of the present embodiment. In Figure 13 , the illustration of a part of the structure common to the semiconductor manufacturing apparatus 100 of the first embodiment is omitted. In addition, in Figure 13 , the XYZ orthogonal coordinate axes are appropriately shown for the sake of making the directional relationship of the structure clear. Here, the XY plane represents the horizontal plane, and the +Z direction represents the vertical upward direction.

[0228] The ultraviolet irradiation section 210 is disposed above the substrate holding section 110 inside the chamber 170 in a manner capable of irradiating the surface Wf of the substrate W held by the substrate holding section 110 with ultraviolet light in the direction indicated by the arrow Z of Figure 13 . The ultraviolet irradiation section 210 has at least a plurality of light source sections 211 and a quartz glass 212.

[0229] Figure 13 The light source section 211 shown is a linear light source and is disposed so that the length direction thereof is parallel to the direction indicated by the arrow Y of Figure 13 . In addition, the light source sections 211 are arranged in the direction indicated by the arrow X so as to be equidistant from each other. However, the light source sections 211 of the present embodiment are not limited to this manner. For example, the light source sections can be annular, and light source sections having different diameters can be disposed in a concentric circular manner. In addition, the light source sections can be point light sources. In this case, it is preferable that the plurality of light source sections be disposed so as to be equidistant from each other in the plane.

[0230] There is no particular limitation on the kind of the light source section 211, 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) or the like can be used. In addition, the plurality of light source sections 211 can be the same kind or different kinds. In the case where the light source sections 211 use a plurality of different kinds of light source sections, it is possible to dispose them so as to be different from each other in peak wavelength or light intensity or the like.

[0231] The quartz glass 212 is disposed between the light source sections 211 and the substrate W. The quartz glass 212 is a plate-shaped body and is disposed so as to be parallel to the horizontal direction. In addition, the quartz glass 212 has light transmission, heat resistance, and corrosion resistance with respect to ultraviolet light, and is capable of transmitting the ultraviolet light irradiated from the light source sections 211 to the surface Wf of the substrate W. Furthermore, the quartz glass 212 protects the light source sections 211 from the atmosphere inside the chamber 170.

[0232] <Etching Processing Unit>

[0233] The etching unit in this embodiment is a batch processing unit for etching the etched layer, and performs etching step S2' on the substrate W in the substrate processing unit where SAM is formed. The etching unit is as follows: Figure 14 and Figure 15 As shown, it includes at least: a substrate conveying section (not shown), a lifter 220, and a processing tank 230 for storing etching solution. Figure 14 This is a side view showing the schematic structure of the elevator 220 in the semiconductor manufacturing apparatus of this embodiment. Additionally, Figure 15 This is a cross-sectional view showing the case where a plurality of substrates W having SAM formed thereon in this embodiment are immersed in an etching solution.

[0234] The substrate transport unit transports the substrate W, on which SAM has been formed, from the substrate processing unit to the etching processing unit. The substrate transport unit may include, for example, a multi-joint robot capable of transporting the substrate W. At the top of this multi-joint robot is a transport arm capable of loading the substrate W in a horizontal position at a time.

[0235] Lifter 220 Figure 14 As shown, the device includes a flat backplate portion 221, a plurality of (3) retaining rods 222, and a lifting mechanism (not shown). The backplate portion 221 is vertically mounted, and at its lower end, the retaining rods 222 extend in one direction at right angles to the backplate portion 221. A plurality of grooves 223 are arranged on the retaining rods 222 in their extending direction. Furthermore, the plurality of grooves 223 are arranged at equal intervals, spaced apart from each other. Further, each groove 223 extends in a direction perpendicular to the extending direction of the retaining rods 222, and can fit into the plurality of substrates W in an upright position. Thus, the retaining rods 222 can abut against the group of support substrates W from below in an upright position and hold them together. In addition, there is no particular limitation on the number of retaining rods 222. In addition, there is no particular limitation on the number of grooves 223 provided on the retaining rods 222, as long as they are appropriately set according to the number of substrates W to be held. In addition, the lifting mechanism allows the lift 220 to... Figure 15 The elevator moves up or down in the Z direction as shown. This allows the lifter 220, which holds the substrate W group together, to move or be removed from inside the processing tank 230.

[0236] Processing tank 230, etc. Figure 15As shown, it is provided with an injection pipe 231 that supplies etching liquid into the processing tank 230, an inner tank 232 that stores the etching liquid, and an outer tank 233 that is provided to the peripheral portion of the upper opening of the inner tank 232. The injection pipe 231 is provided to the bottom of the inner tank 232, and can achieve the upward flow supply of the etching liquid to the inner tank 232. In addition, the outer tank 233 can recover the etching liquid that overflows from the inner tank 232. The injection pipe 231 can be connected to the etching liquid storage portion 161 described in the first embodiment via the discharge pipe 169, for example.

[0237] (Other matters)

[0238] In the above description, the most preferred embodiment of the present application was described. However, the present application is not limited to this embodiment. For example, in the first embodiment, the case where the etching process of the SiN2 layer is performed using the single wafer type was described, but the etching process can also be performed using the batch type described in the second embodiment. In addition, in the first embodiment, the case where the surface modification process is performed using the wet method was described, but the surface modification process can also be performed using the dry method based on ultraviolet irradiation described in the second embodiment. Even in these methods, compared to the conventional film formation method, a film having a high film density and excellent compactness can be formed on the surface of the substrate in a short time with high efficiency, the generation of film defects is well suppressed or reduced, and the SAM having excellent protection performance.

[0239] [Examples]

[0240] Hereinafter, a preferred example of the present application is described in detail by way of illustration. However, the materials or amounts, conditions, and the like described in this example are not limited to these unless otherwise specifically described.

[0241] (Example 1)

[0242] A substrate on the surface of which a SiO2 film (film thickness 100 nm) was formed was prepared, and immersed in a hydrogen fluoride aqueous solution (pretreatment liquid) for 1 minute (pretreatment process). As the hydrogen fluoride aqueous solution, a solution in which the volume ratio of hydrogen fluoride and DIW was hydrogen fluoride: DIW = 1:100 was used.

[0243] Next, the substrate taken out from the hydrogen fluoride aqueous solution was immersed in a surface modification liquid for 10 minutes (surface modification process). As the surface modification liquid, SC-1 (ammonia water (NH3 concentration 28%): hydrogen peroxide water (H2O2 concentration 30%): DIW = 1:4:20 in terms of volume ratio) was used.

[0244] On the other hand, in addition to the surface modification process of the substrate, preparation of the first treatment liquid was also performed. That is, 100 ppm of water was added to toluene as an organic solvent under the conditions of a temperature of 23°C and normal pressure in a closed container in a stationary state. Further, with respect to the mixed liquid of toluene and water, ultrasonic waves were applied for 30 minutes in a stationary state. Thereby, a dispersion liquid in which water was uniformly dispersed in toluene as a main solvent was prepared. As the application conditions of the ultrasonic waves, a frequency of 45 Hz was set. Next, octadecyltrichlorosilane (C 18 H 37 SiCl3) as a SAM formation material was added to the dispersion liquid in a stationary state under the conditions of a temperature of 23°C and normal pressure, thereby preparing the first treatment liquid (first treatment liquid preparation process). The content (concentration) of octadecyltrichlorosilane was set to 5% by mass with respect to the total mass of the first treatment liquid.

[0245] Next, the substrate lifted from the surface modification liquid was immersed in the first treatment liquid for 5 minutes, and a SAM (thickness of about 1 nm) was formed on the SiO2 film surface of the substrate (first contact process). Next, the substrate lifted from the first treatment liquid was immersed in toluene as a removal liquid for 1 minute, and unadsorbed SAM formation material remaining on the surface of the substrate was removed (removal process). Further, with respect to the substrate lifted from the toluene, the surface on which the SAM was formed was blown with nitrogen to perform drying (drying process). The temperature of the nitrogen was set to room temperature, and the drying time was set to 1 minute.

[0246] Next, the substrate after the drying process was immersed in the second treatment liquid for 5 minutes, and densification treatment of the SAM was performed (second contact process). As the second treatment liquid, the same liquid as the first treatment liquid was used. Next, the substrate lifted from the second treatment liquid was immersed in toluene as a removal liquid for 1 minute, and unadsorbed SAM formation material remaining on the surface of the substrate was removed (removal process). Further, with respect to the substrate lifted from the toluene, the surface on which the SAM was formed was blown with nitrogen to perform drying (drying process). The temperature of the nitrogen was set to room temperature, and the drying time was set to 1 minute.

[0247] Next, etching treatment was performed on the obtained sample. Specifically, the substrate was immersed in an etching liquid, and a region in the surface of the substrate that was not protected by the SAM was etched. As the etching conditions, the immersion time (etching treatment time) in the etching liquid was set to 195 seconds in such a manner that the etching amount of SiO2 was about 10 nm. In addition, as the etching liquid, a hydrogen fluoride aqueous solution was used, and the volume ratio of hydrogen fluoride to DIW was set to hydrogen fluoride: DIW = 1: 100.

[0248] Next, after the substrate lifted from the etching solution is immersed in the DIW, the substrate is lifted from the DIW (rinsing process using the DIW), and nitrogen is blown to the surface on which the etching treatment is performed to perform drying (drying process). The temperature of the nitrogen is set to room temperature.

[0249] (Example 2)

[0250] In this example, the SAM-forming material of the second treatment solution uses trichloropropylsilane (C3H7SiCl3). Other than this, the sample is produced in the same manner as in Example 1, and the obtained sample is subjected to the etching treatment.

[0251] (Example 3)

[0252] In this example, the SAM-forming material of the second treatment solution uses trichloromethylsilane (CH3SiCl3). Other than this, the sample is produced in the same manner as in Example 1, and the obtained sample is subjected to the etching treatment.

[0253] (Example 4)

[0254] In this example, the cycle of the second contact process, and the removal process and the drying process performed thereafter is repeated twice. In addition, in the second contact process of the second time, the SAM-forming material of the second treatment solution uses decyltrichlorosilane (C 10 H 21 SiCl3). Other than this, the sample is produced in the same manner as in Example 1, and the obtained sample is subjected to the etching treatment.

[0255] (Example 5)

[0256] In this example, the cycle of the second contact process, and the removal process and the drying process performed thereafter is repeated twice. In addition, in the second contact process of the second time, the SAM-forming material of the second treatment solution uses trichloropropylsilane (C3H7SiCl3). Other than this, the sample is produced in the same manner as in Example 1, and the obtained sample is subjected to the etching treatment.

[0257] (Example 6)

[0258] In this example, the cycle of the second contact process, and the removal process and the drying process performed thereafter is repeated twice. In addition, in the second contact process of the second time, the SAM-forming material of the second treatment solution uses trichloromethylsilane (CH3SiCl3). Other than this, the sample is produced in the same manner as in Example 1, and the obtained sample is subjected to the etching treatment.

[0259] (Comparative Example 1)

[0260] In this comparative example, the second contact process and the removal process and the drying process performed thereafter were not performed. Other than this, the sample was produced in the same manner as in Example 1, and further, the etching treatment was performed on the obtained sample.

[0261] (Evaluation of compactness of SAM)

[0262] For each sample of Examples 1 to 6 and Comparative Example 1, the area ratio (%) of the film defect of the SAM was calculated, and the compactness of the SAM was evaluated.

[0263] That is, the SAM of each sample was imaged using an atomic force microscope (AFM) (trade name: Dimension Icon, manufactured by Bruker Japan, Inc.), and an observation image (AFM image) of 500 nm square was obtained. Next, after binarizing each of the obtained observation images, image processing was performed to map the film defect, and thus the site (region) of the film defect of the SAM was determined. The determination of the site (region) of the film defect of the SAM using mapping was performed by considering that the film thickness of the SAM was about 1 nm, and the image processing was performed to map the defect at a position of less than 1 nm in depth from the surface of the SAM. Thus, the site (region) of more than 1 nm in depth from the surface of the SAM, and more specifically, the site subjected to etching was mapped as the region of the film defect of the SAM, and was not included in the area thereof. Next, for the region of the film defect of the SAM determined by the image processing, the area thereof was calculated, and the ratio with respect to the area of the entire region in the observation image was calculated. The results are shown in Table 1.

[0264] (Result)

[0265] As shown in Table 1, it was confirmed that the area ratio of the film defect of the SAM was reduced in Examples 1 to 6 in which the compactness treatment by the second contact process was performed, as compared with Comparative Example 1 in which the second contact process was not performed, and each of Examples 1 to 6 had good compactness. Further, in Examples 2 and 3, the molecule having a shorter molecular chain length than the SAM-forming material of the first treatment solution was used as the SAM-forming material of the second treatment solution used in the second contact process, and thus the area ratio of the film defect of the SAM was reduced as compared with Example 1. In addition, in Examples 4 to 6, the cycle of the second contact process and the removal process and the drying process performed thereafter was repeated twice, and thus the area ratio of the film defect of the SAM was further reduced as compared with Examples 2 and 3.

[0266] In addition, according to the results of these embodiments, it was found that, in a case where the threshold value of the area ratio (%) of film defects of the SAM is set to, for example, 15% or less, as shown in Embodiment 1, it is sufficient that the second molecule used in the second contact process is at least the same kind as the molecule used in the first contact process. In addition, it was found that, for example, in a case where the threshold value is set to 10% or less, as shown in Embodiments 2 or 3, it is sufficient that, as the second molecule used in the second contact process, a molecule having a shorter molecular chain length than the molecule used in the first contact process is used, or as shown in Embodiment 4, in a case where the second contact process is performed a plurality of times and the second contact process is performed a second time, as the second molecule, a molecule having a shorter molecular chain length than the molecule used in the first contact process is used. Furthermore, it was found that, in a case where the threshold value is set to 5% or less, as shown in Embodiments 5 or 6, it is sufficient that, in a case where the second contact process is performed a plurality of times and the second contact process is performed a second time, as the second molecule, a molecule having a further shorter molecular chain length than the molecule used in the first contact process is used.

[0267] [Table 1]

[0268] Explanation of Reference Numerals: 1: SiO2 layer (protective layer) 2: SiN layer (etching layer) 3: laminate 4: storage trench 5: first molecule 6: SAM (self-assembled monomolecular film) 7: film defect 8: second molecule 100: semiconductor manufacturing apparatus 110: substrate holding portion 120: pretreatment liquid supply portion 121: pretreatment liquid storage portion 130: surface modification liquid supply portion 131: surface modification liquid storage portion 140: first treatment liquid supply portion 141: first treatment liquid storage portion 150: second treatment liquid supply portion 151: second treatment liquid storage portion 160: etching liquid supply portion 161: etching liquid storage portion 190: rotation drive portion 200: substrate processing unit 210: ultraviolet irradiation portion 220: lifter 230: treatment tank 231: injection pipe 232: inner tank 233: outer tank 300: control section S1, SAM (self-assembled monolayer) formation step S2, S2': etching step S101: pretreatment step S102: surface modification step S103: first treatment liquid preparation step S104: first contact step S105: second treatment liquid preparation step S106: second contact step W: substrate Wf: surface of the substrate.

Claims

1. A substrate processing method, wherein a self-assembled monolayer is formed on the surface of a substrate, wherein, The substrate processing method includes: The surface modification process involves modifying the surface of the substrate to enable the formation of the self-assembled monolayer. In the first contact process, a first processing liquid containing a first molecule capable of forming the self-assembled monomolecular film is brought into contact with the surface of the substrate after the surface modification process to form the self-assembled monomolecular film. The second contact process involves contacting a second treatment liquid containing a second molecule of the same or different kind as the first molecule with the surface of the substrate after the first contact process, thereby causing the second molecule to be chemically adsorbed in the region where the self-assembled monolayer has not been formed. Perform the second contact process at least once until the area ratio (%) of the film defects of the self-assembled monomolecular film formed on the surface of the substrate reaches below an arbitrarily set threshold.

2. The substrate processing method according to claim 1, wherein, The second molecule has the same or shorter molecular chain length as the first molecule.

3. The substrate processing method according to claim 1, wherein, In the case of performing the second contact process multiple times, the second molecule used in the earlier process has the same or longer molecular chain length as the second molecule used in the later process.

4. The substrate processing method according to claim 1, wherein, The first molecule and the second molecule have functional groups capable of undergoing dehydration condensation reactions with hydroxyl groups; The surface modification process is a process of imparting the hydroxyl groups to the surface of the substrate; The first contact process and the second contact process are processes in which the first molecule or the second molecule is chemically adsorbed onto the surface of the substrate by the dehydration condensation reaction between the functional group of the first molecule or the second molecule and the hydroxyl group on the surface of the substrate.

5. The substrate processing method according to claim 4, wherein, The surface modification process involves contacting a surface modification liquid containing an alkaline solution with the surface of the substrate, or irradiating the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms, thereby imparting the hydroxyl groups to the surface of the substrate.

6. A method for manufacturing a semiconductor device, comprising processing a substrate on which a laminate is disposed on its surface. The laminate comprises a structure consisting of alternating layers of a protected layer that becomes the object of etching and an etched layer that becomes the object of etching. The method for manufacturing the semiconductor device includes: The process of selectively forming a self-assembled monolayer on at least the surface of the protected layer; and The process of selectively etching the layer to be etched, using the self-assembled monolayer as a protective layer; The process of forming the self-assembled monolayer includes: The surface modification process involves modifying the surface of the protected layer to enable the formation of the self-assembled monolayer. In the first contact step, a first processing liquid containing a first molecule capable of forming the self-assembled monolayer is brought into contact with the surface of the protected layer after the surface modification step to form the self-assembled monolayer; and The second contact process involves contacting a second treatment liquid containing a second molecule of the same or different kind as the first molecule with the surface of the substrate after the first contact process, thereby causing the second molecule to be chemically adsorbed in the region where the self-assembled monolayer has not been formed. Perform the second contact process at least once until the area ratio (%) of the membrane defects of the self-assembled monomolecular membrane formed on the surface of the protected layer reaches below an arbitrarily set threshold.

7. The method for manufacturing a semiconductor device according to claim 6, wherein, The second molecule has the same or shorter molecular chain length as the first molecule.

8. The method for manufacturing a semiconductor device according to claim 6, wherein, In the case of performing the second contact process multiple times, the second molecule used in the earlier process has the same or longer molecular chain length as the second molecule used in the later process.

9. The method for manufacturing a semiconductor device according to claim 6, wherein, The first molecule and the second molecule have functional groups capable of undergoing dehydration condensation reactions with hydroxyl groups; The surface modification process is a process of imparting the hydroxyl groups to the surface of the protected layer; The first contact step and the second contact step are steps in which the first molecule or the second molecule is chemically adsorbed onto the surface of the protected layer by the dehydration condensation reaction between the functional groups of the first molecule or the second molecule and the hydroxyl groups on the surface of the protected layer.

10. The method of manufacturing a semiconductor device according to claim 9, wherein, The surface modification process involves contacting a surface modification liquid containing an alkaline solution with the surface of the substrate, or irradiating the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms, thereby imparting the hydroxyl groups to the surface of the substrate.

11. A substrate processing apparatus for forming a self-assembled monolayer on the surface of a substrate, wherein, The substrate processing apparatus includes: The surface modification section modifies the surface of the substrate to enable the formation of the self-assembled monomolecular film. The first processing liquid supply unit supplies a first processing liquid containing a first molecule capable of forming the self-assembled monomolecular film to the surface of the substrate that has been surface-modified by the surface modification unit, thereby forming the self-assembled monomolecular film. as well as The second processing liquid supply unit supplies a second processing liquid containing a second molecule of the same or different kind as the first molecule to the surface of the substrate on which the self-assembled monomolecular film is formed, thereby causing the second molecule to be chemically adsorbed in the area where the self-assembled monomolecular film is not formed. The second processing liquid supply unit supplies the second processing liquid at least once until the area ratio (%) of the film defects of the self-assembled monomolecular film formed on the surface of the substrate reaches below an arbitrarily set threshold.

12. The substrate processing apparatus according to claim 11, wherein, The second molecule has the same or shorter molecular chain length as the first molecule.

13. The substrate processing apparatus according to claim 11, wherein, When the second processing liquid is supplied to the surface of the substrate multiple times by the second processing liquid supply unit, the second molecules contained in the first supplied second processing liquid have the same or longer molecular chain length as the second molecules contained in the later supplied second processing liquid.

14. The substrate processing apparatus according to claim 11, wherein, The first molecule and the second molecule have functional groups capable of undergoing dehydration condensation reactions with hydroxyl groups; The surface modification section performs the surface modification by imparting the hydroxyl groups to the surface of the substrate; The first processing liquid supply unit and the second processing liquid supply unit chemically adsorb the first molecule or the second molecule onto the surface of the substrate through a dehydration condensation reaction between the functional groups of the first molecule or the second molecule and the hydroxyl groups on the surface of the substrate.

15. The substrate processing apparatus according to claim 14, wherein, The surface modification section is either a surface modification liquid supply section or an ultraviolet irradiation section; The surface modification liquid supply unit imparts hydroxyl groups to the surface of the substrate by supplying a surface modification liquid containing an alkaline solution to the surface of the substrate. The ultraviolet irradiation section imparts hydroxyl groups to the surface of the substrate by irradiating the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms.

16. A semiconductor manufacturing apparatus for processing a substrate on which a laminate is disposed on its surface. The laminate comprises a structure consisting of alternating layers of a protected layer that becomes the object of etching and an etched layer that becomes the object of etching. The semiconductor manufacturing apparatus has: The surface modification section modifies the surface of the protected layer to enable the formation of a self-assembled monolayer. The first processing liquid supply unit supplies a first processing liquid containing a first molecule capable of forming the self-assembled monomolecular film to the surface of the protected layer that has been surface-modified by the surface modification unit, thereby forming the self-assembled monomolecular film. The second processing liquid supply unit supplies a second processing liquid containing a second molecule of the same or different kind as the first molecule to the surface of the protected layer on which the self-assembled monomolecular film is formed, thereby causing the second molecule to be chemically adsorbed in the area where the self-assembled monomolecular film is not formed. as well as The etching section uses the self-assembled monolayer as a protective layer to selectively etch and remove the etched layer; The second processing liquid supply unit supplies the second processing liquid at least once until the area ratio (%) of the membrane defects of the self-assembled monomolecular membrane formed on the surface of the protected layer reaches below an arbitrarily set threshold.

17. A semiconductor manufacturing apparatus for processing a substrate on which a laminate is disposed on its surface, wherein, The laminate comprises a structure consisting of a protected layer that serves as the object to be etched and an etched layer that serves as the object to be etched, which are alternately stacked. The semiconductor manufacturing apparatus has: A substrate processing unit selectively forms a self-assembled monomolecular film on at least the surface of the protected layer; as well as The etching unit selectively etches and removes the layer to be etched, using the self-assembled monolayer as a protective layer. The substrate processing unit has: The surface modification section modifies the surface of the protected layer to enable the formation of the self-assembled monolayer. The first processing liquid supply unit supplies a first processing liquid containing a first molecule capable of forming the self-assembled monomolecular film to the surface of the protected layer that has been surface-modified by the surface modification unit, thereby forming the self-assembled monomolecular film. as well as The second processing liquid supply unit supplies a second processing liquid containing a second molecule of the same or different kind as the first molecule to the surface of the protected layer on which the self-assembled monomolecular film is formed, thereby causing the second molecule to be chemically adsorbed in the area where the self-assembled monomolecular film is not formed. The second processing liquid supply unit supplies the second processing liquid at least once until the area ratio (%) of the membrane defects of the self-assembled monomolecular membrane formed on the surface of the protected layer reaches below an arbitrarily set threshold.

18. The semiconductor manufacturing apparatus according to claim 16 or 17, wherein, The second molecule has the same or shorter molecular chain length as the first molecule.

19. The semiconductor manufacturing apparatus according to claim 16 or 17, wherein, When the second processing liquid supply unit supplies the second processing liquid to the surface of the protected layer multiple times, the second molecules contained in the first supplied second processing liquid have the same or longer molecular chain length as the second molecules contained in the later supplied second processing liquid.

20. The semiconductor manufacturing apparatus according to claim 16 or 17, wherein, The first molecule and the second molecule have functional groups capable of undergoing dehydration condensation reactions with hydroxyl groups; The surface modification section performs the surface modification by imparting the hydroxyl groups to the surface of the substrate; The first processing liquid supply unit and the second processing liquid supply unit chemically adsorb the first molecule or the second molecule onto the surface of the substrate through a dehydration condensation reaction between the functional groups of the first molecule or the second molecule and the hydroxyl groups on the surface of the substrate.

21. The semiconductor manufacturing apparatus according to claim 16 or 17, wherein, The surface modification section is either a surface modification liquid supply section or an ultraviolet irradiation section; The surface modification liquid supply unit imparts hydroxyl groups to the surface of the protected layer by supplying a surface modification liquid containing an alkaline solution to the surface of the protected layer. The ultraviolet irradiation section imparts hydroxyl groups to the surface of the protected layer by irradiating the surface of the substrate with ultraviolet light in an atmosphere containing oxygen atoms.

Images