Surface treatment method for semiconductor substrate and surface treatment composition

Abstract

A surface treatment method for a semiconductor substrate according to the present invention is a treatment method for treating a main surface of a semiconductor substrate that has, on the main surface of the substrate, a pattern-formed region in which a pattern having a protrusion-and-recess structure having a pattern dimension of at most 30 nm is formed, and a pattern non-formed region in which no pattern is formed. The surface treatment method includes a surface treatment step for bringing a silylating agent-containing surface treatment agent composition into contact with the pattern-formed region and the pattern non-formed region on the main surface of the semiconductor substrate, wherein, on the surface of the pattern non-formed region after the surface treatment step, the IPA contact angle with respect to 2-propanol is at least 2° at a room temperature of 25 °C, and / or the water contact angle with respect to pure water is at least 50° at a room temperature of 25 °C.

Description

[Technical Field]

[0001] The present invention relates to a surface treatment method for a semiconductor substrate and a surface treatment composition. [Background technology]

[0002] Various surface treatment methods for semiconductor substrates have been developed to date. One known example of this type of technology is described in Patent Document 1. Patent Document 1 describes a method in which, apart from a Si substrate having a Si pillar pattern formed all over its surface, a surface treatment is performed on a dummy substrate having a SiO2 film or SiN film formed on a Si substrate, and the water contact angle of the dummy substrate having no pattern is evaluated (Examples of Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] WO2018 / 175682 Summary of the Invention [Problem to be solved by the invention]

[0004] However, as a result of investigations by the present inventors, it has been found that the surface treatment method for semiconductor substrates described in Patent Document 1 has room for improvement in terms of production controllability and production stability. [Means for solving the problem]

[0005] As a result of further investigation, the present inventors have obtained the following findings. By using a semiconductor substrate having a pattern formation region on its main surface on which a fine pattern is formed and a pattern non-formation region, it is possible to perform a surface treatment on the surface of the pattern formation region, and also to measure the contact angle with 2-propanol (hereinafter referred to as the IPA contact angle) or the contact angle with pure water (hereinafter referred to as the water contact angle) on the surface of the pattern non-formation region after the surface treatment. In other words, it is possible to evaluate the surface treatment on the pattern and the IPA contact angle or water contact angle on the surface after the surface treatment on the same semiconductor substrate, which makes it easier to manage the manufacturing process compared to when a separate dummy substrate is used. Based on this finding, the present inventors conducted further intensive research and found that by using the IPA contact angle or water contact angle on the surface in the pattern non-forming region as an index, it is possible to stably evaluate the rate of pattern collapse in the pattern forming region, and further that by keeping the IPA contact angle or water contact angle within a predetermined range, it is possible to suppress pattern collapse, thereby completing the present invention.

[0006] According to the present invention, 1. A method for processing a main surface of a semiconductor substrate having a pattern-formed region on a main surface of the substrate, the pattern-formed region having a pattern having a relief structure with a pattern dimension of 30 nm or less, and a pattern-non-formed region where the pattern is not formed, the method comprising: a surface treatment step of contacting the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate with a surface treatment agent composition containing a silylating agent, On the surface of the pattern non-forming region after the surface treatment step, The contact angle of IPA with 2-propanol is 2° or more at room temperature (25°C), and / or The water contact angle with pure water is 50° or more at room temperature of 25°. A processing method is provided.

[0007] Further, according to the present invention, A surface treatment agent composition used for treating a main surface of a semiconductor substrate, the main surface of the substrate having a pattern-formed region in which a pattern having a relief structure with a pattern dimension of 30 nm or less is formed, and a pattern-non-formed region in which the pattern is not formed, comprising: a silylating agent, The IPA contact angle, as determined by the following procedure, is 2° or greater, and / or The water contact angle, determined by the following procedure, is 50° or more. A surface treatment composition is provided. (procedure) The surface treatment agent composition is brought into contact with the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate. After contacting the surface treatment agent composition, on the surface of the pattern non-forming region, The contact angle with 2-propanol was measured at room temperature of 25°C, and the measured value was taken as the IPA contact angle (°). The contact angle with pure water is measured at room temperature of 25°C, and the measured value is taken as the water contact angle (°). [Effects of the Invention]

[0008] According to the present invention, there are provided a method for treating the surface of a semiconductor substrate, which is excellent in production controllability and production stability, and a surface treatment composition used therein. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 2 is a top view schematically illustrating the configuration of a semiconductor substrate. [Figure 2] FIG. 2 is a cross-sectional view schematically illustrating the configuration of a semiconductor substrate. [Figure 3] 1A to 1C are cross-sectional views schematically illustrating a manufacturing process of a semiconductor substrate. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by similar reference numerals, and descriptions thereof will be omitted where appropriate. Furthermore, the drawings are schematic diagrams and do not correspond to actual dimensional proportions.

[0011] The surface treatment method for a semiconductor substrate of this embodiment is a treatment method for treating the main surface of a semiconductor substrate having, on the main surface of the substrate, a pattern-formed region where a pattern having a concave-convex structure with a pattern dimension of 30 nm or less is formed, and a pattern-non-formed region where no pattern is formed. This treatment method includes a surface treatment step of contacting a pattern formation region and a pattern non-formation region of a main surface of a semiconductor substrate with a surface treatment agent composition containing a silylating agent, and after the surface treatment step, the surface of the pattern non-formation region has an IPA contact angle with 2-propanol of 2° or more at room temperature and 25° and / or a water contact angle with pure water of 50° or more at room temperature and 25°.

[0012] The surface treatment method disclosed in the examples of Patent Document 1 is a method in which a smooth dummy substrate surface is treated with a surface treatment composition to evaluate the water contact angle, and separately, a patterned substrate surface is treated with the surface treatment composition to evaluate the collapse-free rate of the pattern. In order to confirm whether a predetermined water repellency is exhibited, it is necessary to separately evaluate the water contact angle using a smooth dummy substrate, and the present inventors have found that a more efficient manufacturing method (simplification of process management) is desired.

[0013] According to the findings of the inventors, the processing method of this embodiment is a more efficient manufacturing method that processes a semiconductor substrate having a smooth, non-patterned region where no pattern is formed, such as around an orientation flat or notch or on the outer periphery of the wafer, and evaluates the contact angle in the non-patterned region of the substrate and evaluates the collapse-free rate in the patterned region where a pattern is formed. In other words, compared to conventional, complicated manufacturing methods that separately evaluate water contact angles using a smooth, dummy substrate, the manufacturing method of the present disclosure does not require evaluation of a smooth, dummy substrate, and can evaluate a portion of the surface after surface treatment (the surface of the non-patterned region that has been dried after surface treatment and rinsing), making it a more efficient manufacturing method (with simplified process control). The area of ​​the non-patterned region per one contact angle measurement point on the semiconductor substrate to be processed is 200 mm 2 More than 300mm is preferable 2 More than 350mm is preferable. 2 More preferably, 400mm or more 2 The above is particularly preferred.

[0014] Furthermore, isopropanol (IPA) or water may be used as a rinse solution after the surface treatment (the "second rinse solution" described below). In such an embodiment, the present inventors have found that in order to further reduce the capillary force acting on the pattern when the IPA or water dries and thus further suppress collapse of the pattern, it is desirable that the surface treatment agent layer formed by the surface treatment have a larger IPA contact angle and / or a larger water contact angle.

[0015] Furthermore, in some embodiments, the rinse solution after the surface treatment (the "second rinse solution" described below) may be water and IPA rinsed sequentially (for example, "surface treatment → water rinse → IPA rinse" or "surface treatment → IPA rinse → water rinse"), and the inventors have found that in such embodiments, it is desirable for the IPA contact angle and water contact angle to be large.

[0016] In another embodiment of the present invention, a processing method includes: 1. A method for processing a main surface of a semiconductor substrate having a pattern-formed region on a main surface of the substrate, the pattern-formed region having a pattern having a relief structure with a pattern dimension of 30 nm or less, and a pattern-non-formed region where the pattern is not formed, the method comprising: a surface treatment step of contacting the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate with a surface treatment agent composition containing a silylating agent; and on the surface of the pattern non-forming region after the surface treatment step, The contact angle of IPA with 2-propanol is 2° or greater, and / or An evaluation process to determine whether the water contact angle with pure water is 50° or more Includes. In the evaluation step, the state of modification of the semiconductor substrate surface can be evaluated using the IPA contact angle or water contact angle as an index, and if it is determined that one or both of these are equal to or greater than a predetermined value, the subsequent substrate processing process can proceed. Subsequent processes include, for example, a second rinsing step, a drying step, a removal step, and known substrate surface treatments that have not yet been performed. Furthermore, if the angle is not equal to or greater than the predetermined value, the evaluation step may be performed after another surface treatment step. This eliminates the need for separate contact angle evaluation using a dummy substrate, and makes it possible to determine the progress of the process on the production line, simplifying production management. Furthermore, after the process has begun, pattern collapse in the pattern formation area can be suppressed, improving production stability.

[0017] In the present invention, on the surface of the pattern non-forming region of the main surface after the surface treatment, The IPA contact angle is 2° or more, preferably 3° or more at room temperature (25°C), and / or The water contact angle at room temperature (25°) is 50° or more, preferably 55° or more, and more preferably 60° or more. This can reduce the rate of pattern collapse in the pattern formation region. On the other hand, the IPA contact angle may be, for example, 10° or less, and the water contact angle may be, for example, 110° or less, or 99° or less. The IPA contact angle and the water contact angle can be measured on the surface of the surface treatment agent layer formed in the non-pattern formation region by the surface treatment step. The timing of measurement after surface treatment may be immediately after the surface treatment step in which the surface treatment agent composition is brought into contact with the main surface of the semiconductor substrate, or may be immediately after the post-rinse step performed after the surface treatment step, or immediately after the subsequent drying step. The timing for measuring the contact angle may be immediately before the surface treatment agent layer is removed, or immediately after the surface treatment agent composition or other liquids are removed from the surface of the pattern non-forming region. At least one of these timings may be used. In this specification, immediately after or immediately before means within 24 hours, preferably within 2 hours, and particularly preferably within 30 minutes.

[0018] Furthermore, according to the surface treatment method of the present invention, the standard deviation of the IPA contact angles at 10 predetermined locations in the pattern non-forming region can be configured to be, for example, 2° or less, and the difference between the maximum and minimum IPA contact angles can be configured to be, for example, 5° or less. Similarly, the standard deviation of the water contact angles at 10 predetermined locations in the pattern non-forming region can be set to, for example, 2° or less, and the difference between the maximum and minimum water contact angles can be set to, for example, 5° or less.

[0019] BACKGROUND ART It is known that in the manufacturing process of forming semiconductor elements on a semiconductor substrate (wafer), foreign matter (particles) such as metal particles or inorganic particles adhere to the bevel or the like located at the edge of the semiconductor wafer. By forming a surface treatment agent layer having the above-described IPA contact angle and / or water contact angle on the main surface of the non-pattern-forming region and / or the bevel region, it is possible to reduce the re-adhesion of foreign matter to the bevel region or the non-pattern-forming region.

[0020] The surface treatment agent composition of the present embodiment is used to treat the main surface of a semiconductor substrate having, on the main surface of the substrate, a pattern-forming region where a pattern having an uneven structure with a pattern dimension of 30 nm or less is formed, and a pattern-non-forming region where no pattern is formed. Such a surface treatment agent composition contains a silylating agent and is configured so that the IPA contact angle measured by the following procedure is 2° or more and / or the water contact angle measured by the following procedure is 50° or more.

[0021] The IPA contact angle and the water contact angle are determined by the following procedure. The surface treatment composition is brought into contact with the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate. After contacting the surface treatment composition with the surface of the pattern non-forming region, The contact angle when using 2-propanol was measured at room temperature of 25°C, and the value was taken as the IPA contact angle (°). The contact angle when using pure water is measured at room temperature of 25°C, and this value is taken as the water contact angle (°).

[0022] The IPA contact angle or water contact angle is measured by dropping a 1 μl droplet of 2-propanol or pure water onto the substrate surface in the non-pattern-forming region, specifically onto the surface of the surface treatment agent layer formed in the non-pattern-forming region, at room temperature of 25°C, with the semiconductor substrate placed at rest on a horizontal table, and measuring the static contact angle 5 seconds later. The above contact angle measurement procedure is commonly used to evaluate the properties of a surface treatment agent composition. In the evaluation process of the above-mentioned processing method, the above-mentioned contact angle measurement procedure may be adopted, applying one of the following measurement conditions: a contact angle measurement temperature of 23°±5°, a droplet volume of 0.1 μl to 5 μl, and a measurement timing of 0.1 seconds to 30 seconds after dropping.

[0023] In this embodiment, the IPA contact angle and / or water contact angle can be controlled by, for example, appropriately selecting the type and blending amount of each component contained in the surface treatment agent composition, the preparation method of the surface treatment agent composition, etc. Among these, for example, appropriately selecting the type of silylating agent and other components, mixing the composition components and using them promptly after preparation, etc. can be mentioned as factors for setting the IPA contact angle and / or water contact angle within a desired numerical range.

[0024] The surface treatment method using the surface treatment agent composition of this embodiment makes it possible to realize a method for manufacturing a semiconductor substrate that is excellent in production controllability and production stability.

[0025] (Method of manufacturing semiconductor substrate) The method for manufacturing a semiconductor substrate according to this embodiment will now be described in detail.

[0026] An example of a method for producing a semiconductor substrate includes a method in which a main surface of a semiconductor substrate is subjected to a pattern formation, a pre-rinse (first rinse) step, a surface treatment step with a surface treatment agent composition, a post-rinse (second rinse) step, a drying step, removal of the surface treatment agent layer, and the like.

[0027] Each step will be explained below with reference to FIGS. Fig. 1 is a top view of a substrate 10 (semiconductor substrate) viewed from a direction perpendicular to a main surface 12. Fig. 2 is a schematic cross-sectional view of the substrate 10 in a predetermined direction. Figs. 3(a) to 3(c) are schematic cross-sectional views of steps in a manufacturing process of a semiconductor substrate.

[0028] First, a substrate 10 having a pattern (relief structure 20) formed on a main surface 12 is prepared.

[0029] In the above-described step of preparing the substrate 10, the following method, which is one example of a method for forming the uneven structure 20 on the surface of the substrate 10, may be used. First, a resist is applied to the wafer surface, and then the resist is exposed through a resist mask. Either the exposed or unexposed resist is removed to create a resist with the desired concave-convex pattern. Alternatively, a resist with a concave-convex pattern can be obtained by pressing a mold with a pattern against the resist. Next, the wafer is etched. At this time, the substrate surface corresponding to the concave portions of the resist pattern is selectively etched. Finally, the resist is peeled off to obtain a wafer (substrate 10) with a concave-convex structure 20 on its surface.

[0030] The wafer on which the uneven structure 20 is formed and the material of the uneven structure 20 are not particularly limited. The wafer may be made of various materials such as silicon wafers, silicon carbide wafers, wafers made of multiple components including silicon element, sapphire wafers, and various compound semiconductor wafers.

[0031] The material of the concave-convex structure 20 may include one or more selected from the group consisting of Si, Ti, Ge, W, and Ru, as well as oxides, nitrides, nitrogen oxides, carbonitrides, and carbonoxides containing at least one of these. For example, the material of the concave-convex structure 20 may include silicon-based materials such as silicon oxide, silicon nitride, polycrystalline silicon, single-crystalline silicon, and silicon germanium, metal-based materials such as titanium nitride, tungsten, ruthenium, tantalum nitride, and tin, combinations of these materials, and resist (photoresist) materials.

[0032] The substrate 10 in FIG. 1 has, on its main surface 12, a pattern-forming region 30 where a pattern (relief structure 20) is formed, and a pattern-non-forming region 32 where no pattern is formed.

[0033] 1 may have a notch 14 formed in part of its peripheral edge. The notch 14 may be a straight notch that indicates the direction of the crystal axis, called an orientation flat, or a V-shaped notch, for positioning purposes in an exposure device or the like.

[0034] The pattern formation region 30 is a region in which one or more concave-convex structures 20 are formed when viewed from a direction perpendicular to the main surface 12, i.e., when viewed from above. The pattern formation region 30 may include an element formation region in which one or more semiconductor elements are formed. The relief structure 20 may be configured as a three-dimensional structure having, for example, one or more structures arranged along the vertical direction of the main surface 12 and / or one or more structures arranged along a horizontal direction perpendicular to the vertical direction. Examples of such three-dimensional structures may constitute at least a part of a logic device or a memory device, such as a FinFET, a nanowire FET, a nanosheet FET, or other multi-gate type FET, a three-dimensional memory cell, etc.

[0035] The pattern non-formation region 32 is a region that is formed in a top view on at least a part of the periphery or the entire periphery of the pattern formation region 30. The pattern non-formation region 32 may be formed continuously with one another or may be formed as a plurality of partitions. The pattern non-forming region 32 has at least a part of a smooth surface region where the relief structure 20 is not formed.

[0036] One or more cut regions for dicing may be formed in the pattern formation region 30 and / or between the pattern formation region 30 and the pattern non-formation region 32.

[0037] FIG. 2 is a cross-sectional view showing an example of the concave-convex structure 20. As shown in FIG. In this embodiment, the pattern dimension of the concave-convex structure 20 can be defined as at least one width dimension in the in-plane direction of the main surface 12 and / or at least one height dimension in the direction perpendicular to the main surface 12. In the cross-sectional structure (in the substrate thickness direction) of the pattern of the concave-convex structure 20, at least one of the pattern dimensions of its width and height, or in the three-dimensional structure (three-dimensional coordinates of X, Y, and Z) of the pattern of the concave-convex structure 20, at least one of the pattern dimensions of its width (length in the X-axis direction), height (length in the Y-axis direction), and depth (length in the Z-axis direction) may be, for example, 30 nm or less, 20 nm or less, or 10 nm or less. This may also be the spacing between patterns. Even when a substrate 10 having such a fine concave-convex structure 20 is used, the surface treatment agent composition of this embodiment can be applied.

[0038] Such a surface treatment agent composition is suitable for use in surface treatment of a substrate 10 having a relief structure 20 with a pattern dimension of 30 nm or less, preferably 20 nm or less.

[0039] The aspect ratio of the protrusions 22 may be, for example, not less than 3, not less than 5, or not less than 10. Even in the concave-convex structure 20 having the protrusions 22 with a fragile structure, pattern collapse can be suppressed. On the other hand, the aspect ratio of the protrusions 22 is not particularly limited, but may be 100 or less. The aspect ratio of the protrusions 22 is expressed as the value obtained by dividing the height of the protrusions 22 by the width of the protrusions 22 .

[0040] 1 and 2, the substrate 10 may have a bevel region 50 formed on at least a portion of the edge of the substrate 10. The substrate 10 in the bevel region 50 may have an inclined surface (bevel) formed on the main surface 12, and may have, for example, a top edge 51, an upper bevel 52, a front shoulder 53, an end surface 54, and a lower bevel 55.

[0041] Subsequently, if necessary, the main surface 12 of the substrate 10 may be contacted with an aqueous cleaning solution (cleaning step). Examples of aqueous cleaning solutions include water, alcohol, an aqueous ammonium hydroxide solution, an aqueous tetramethylammonium solution, an aqueous hydrochloric acid solution, an aqueous hydrogen peroxide solution, an aqueous sulfuric acid solution, and an organic solvent, which may be used alone or in combination of two or more.

[0042] The cleaning step may be carried out once or twice or more times before the surface treatment step or the first rinse step. Other steps may be included between multiple cleaning steps or between a cleaning step and a surface treatment step.

[0043] Subsequently, if necessary, the main surface 12 of the substrate 10 may be brought into contact with a first rinse solution (first rinse step). The first rinse solution may be a cleaning liquid different from the aqueous cleaning solution, such as water, an organic solvent, a mixture thereof, or a mixture of any of these with at least one of an acid, an alkali, a surfactant, and an oxidizing agent. Examples of organic solvents used in the first rinse solution include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, etc. Among these, it is preferable to use at least one organic solvent selected from alcohols having 3 or less carbon atoms, such as methanol, 1-propanol, and 2-propanol (isopropanol).

[0044] Alternatively, multiple types of first rinse solutions may be used. For example, rinsing may be performed in the order of an acidic or alkaline aqueous solution, followed by an organic solvent. Alternatively, an additional aqueous cleaning solution may be added, followed by an acidic or alkaline aqueous solution, followed by an aqueous cleaning solution, followed by an organic solvent.

[0045] The first rinsing step may be performed once or twice or more times after the cleaning step or before the surface treatment step. Other steps may be included between multiple first rinsing steps or between the first rinsing step and the surface treatment step.

[0046] Next, as shown in FIG. 3(a), the main surface 12 of the substrate 10 is brought into contact with the surface treatment agent composition 60 of this embodiment (surface treatment agent composition). The liquid surface treatment agent composition 60 is preferably supplied to the concave-convex structure 20 formed on the surface of the substrate 10. At this time, the surface treatment agent composition 60 may be supplied so as to fill part or all of the recesses 24 of the concave-convex structure 20. The supply of the surface treatment agent composition 60 may be carried out in a state where the first rinse solution or the aqueous cleaning solution is held on the main surface 12. In other words, by replacing the first rinse solution or the aqueous cleaning solution with the surface treatment agent composition 60, it becomes possible to carry out the surface treatment step before the surface of the concave-convex structure 20 on the main surface 12 of the substrate 10 becomes dry.

[0047] The surface treatment agent composition 60 can be supplied by any known means. For example, a single wafer method, represented by a spin method (spin coating method), is preferred, in which wafers are held substantially horizontally one by one and rotated while the composition is supplied near the center of rotation, thereby replacing a cleaning liquid or the like retained in the uneven pattern of the wafer and filling the composition. Alternatively, a batch method may be used in which multiple wafers are immersed in a composition tank, replacing a cleaning liquid or the like retained in the uneven pattern of the wafer, and filling the composition.

[0048] Subsequently, as shown in FIG. 3(b), a surface treatment agent layer 70 can be formed on the main surface 12 of the substrate 10 by bringing the surface treatment agent composition 60 into contact with the main surface 12. If necessary, the formation of the surface treatment agent layer 70 may be promoted by applying known means such as heating, decompression, or drying to the surface treatment agent composition 60 on the main surface 12 .

[0049] The surface treatment agent layer 70 is formed on at least the pattern formation region 30 and the pattern non-formation region 32 on the main surface 12 of the substrate 10. The surface treatment agent layer 70 may be formed on the bevel region 50 on the main surface 12, or may be formed over the entire main surface 12.

[0050] Subsequently, if necessary, the main surface 12 on which the surface treatment agent layer 70 has been formed may be brought into contact with a second rinse liquid (second rinse step). As the second rinse solution, the same as those exemplified as the first rinse solution can be used.

[0051] Alternatively, multiple types of second rinse solutions may be used. For example, rinsing can be performed in the order of water followed by an organic solvent such as isopropanol, or an organic solvent such as isopropanol followed by water.

[0052] The second rinsing step may be performed once or twice or more times after the surface treatment step. Other steps may be included between multiple second rinsing steps or between the second rinsing step and the surface treatment step.

[0053] Subsequently, if necessary, a drying step may be carried out to dry the main surface 12 of the substrate 10. The drying step can remove any liquid present on the major surface 12 of the substrate 10 . As the drying means, for example, known means such as spin drying, IPA (2-propanol) vapor drying, Marangoni drying, heat drying, hot air drying, and vacuum drying may be used.

[0054] The drying step may be performed once or twice or more times, for example, after the surface treatment step or after the second rinsing step. The drying step and the second rinsing step may be repeated alternately.

[0055] Subsequently, as shown in FIG. 3(c), the surface treatment agent layer 70 on the main surface 12 of the substrate 10 may be removed (removal step). Removal methods include heating, UV irradiation, ozone exposure, plasma irradiation, and corona discharge. Treatment with a concentrated fluid (which may contain an acid, base, or oxidizing agent) such as a supercritical fluid, or steam treatment may also be performed. These methods may be used alone or in combination of two or more. These treatments may be performed under atmospheric pressure or reduced pressure.

[0056] In this manner, a semiconductor substrate (substrate 10) using the surface treatment agent composition of this embodiment is obtained.

[0057] 3 is directed to a wafer pattern, but the present invention is not limited thereto. In the substrate manufacturing method of this embodiment, a resist pattern is also targeted, and by using the surface treatment agent composition of the present invention in the cleaning and drying process, it is possible to suppress collapse of the resist pattern.

[0058] Although the manufacturing method has been described in which the supplying step is performed after the cleaning step, the present invention is not limited to this and the supplying step may be performed after various treatments performed on the concave-convex structure 20 . In addition to the above-described steps, the method for manufacturing a substrate may also include one or a combination of two or more known treatments. For example, a surface treatment such as a plasma treatment may be performed after the above-described removal step.

[0059] Next, the surface treatment agent composition used for the surface treatment of the semiconductor substrate will be described.

[0060] The surface treatment agent composition of the present embodiment contains a silylating agent. The silylating agent may be a known silylating agent. For example, a silicon compound represented by the following general formula [1] may be used. These may be used alone or in combination of two or more.

[0061] R 1 a Si(H) b X 4-a-b [1]

[0062] In the above general formula [1], R 1 are each independently an organic group containing a hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms; X are each independently a monovalent organic group in which the element bonded to the Si atom is nitrogen, oxygen, carbon, or halogen; a is an integer of 1 to 3; b is an integer of 0 to 2; and the sum of a and b is 1 to 3.

[0063] R in the above general formula [1] 1 may contain not only hydrogen, carbon, nitrogen, oxygen, and fluorine elements, but also silicon, sulfur, and halogen elements (other than fluorine). In addition, R in the above general formula [1] 1 may contain an unsaturated bond, an aromatic ring, or a cyclic structure. R in the above general formula [1] 1 As, each independently of the other, C e H 2e+1 (e=1~18), and C f F 2f+1 The examples include at least one group selected from CH2CH2 (f=1 to 8). Among these, silicon compounds having a trialkylsilyl group can be used. In addition, R in the above general formula [1] 1 When contains a silicon element, it may have a structure of the following general formula [1-1]. R 1 m X 3-m-n (H) n Si-(CH2) p -Si(H) n X 3-m-n R 1 m [1-1] In the above general formula [1-1], R 1 (However, this R 1 (not including silicon element) and X are the same as those in the above general formula [1], m is an integer of 1 to 2, n is an integer of 0 to 1, the sum of m and n is 1 to 2, p is an integer of 1 to 18, and -(CH2) p The methylene chain represented by - may be substituted with a halogen.

[0064] In X in the above general formula [1], the monovalent organic group in which the element bonded to the Si element is nitrogen, oxygen, or carbon may contain not only hydrogen, carbon, nitrogen, or oxygen elements, but also silicon, sulfur, halogen elements, etc. Examples of the monovalent organic group in which the element bonded to the Si element is nitrogen include an isocyanate group, an amino group, a dialkylamino group, an isothiocyanate group, an azide group, an acetamide group, -NHC(=O)CF3, -N(CH3)C(=O)CH3, -N(CH3)C(=O)CF3, -N=C(CH3)OSi(CH3)3, -N=C(CF3)OSi(CH3)3, -NHC(=O)-OSi(CH3)3, -NHC(=O)-NH-Si(CH3)3, an imidazole ring, a triazole ring, a tetrazole ring, an oxazolidinone ring, a morpholine ring, -NH-C(=O)-Si(CH3)3, -N(S(=O)2R 4 )2(where R 4 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms), and a substituent having a structure of the following general formula [1-2] [ka] (In the above general formula [1-2], R 5 are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms), -N=C(NR 6 2)2, -N=C(NR 6 2)R 6 (where R 6 are each independently selected from a hydrogen group, a -C≡N group, a -NO2 group, and a hydrocarbon group in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and the hydrocarbon group may have oxygen atoms and / or nitrogen atoms. a1 )(R a2 ) (where, the above R a1 represents a hydrogen atom or a saturated or unsaturated alkyl group, and R a2 represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a saturated or unsaturated heterocycloalkyl group. a1 and R a2 may be bonded to each other to form a saturated or unsaturated heterocycloalkyl group having a nitrogen atom.a3 )-Si(R a4 )(R a5 )(R a6 ) (where, the above R a3 represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a trimethylsilyl group, or a dimethylsilyl group, and the R a4 , R a5 and R a6 each independently represents a hydrogen atom or an organic group, R a4 , R a5 and R a6 The total number of carbon atoms contained in is 1 or more. a7 )-C(=O)R a8 (Here, the above R a7 represents a hydrogen atom, a methyl group, a trimethylsilyl group, or a dimethylsilyl group, and R a8 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group, or a trialkylsilylamino group.

[0065] Examples of silylating agents in which X in the above general formula [1] is a monovalent organic group in which the element bonded to the Si element is nitrogen include CH3Si(NH2)3, C2H5Si(NH2)3, C3H7Si(NH2)3, C4H9Si(NH2)3, and C5H 11 Si(NH2)3, C6H 13 Si(NH2)3, C7H 15 Si(NH2)3, C8H 17 Si(NH2)3, C9H 19 Si(NH2)3, C 10 H 21 Si(NH2)3, C 11 H 23 Si(NH2)3, C 12 H 25 Si(NH2)3, C 13 H 27 Si(NH2)3, C 14 H 29 Si(NH2)3, C 15 H 31 Si(NH2)3, C 16 H 33 Si(NH2)3, C 17 H 35 Si(NH2)3, C<h2 style=";text-align:left;direction:ltr"> 18 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 37 <h2 style=";text-align:left;direction:ltr"> Si(NH2)3, (CH3)2Si(NH2)2, C2H5Si(CH3)(NH2)2, (C2H5)2Si(NH2)2, C3H7Si(CH3)(NH2)2, (C3H7)2Si(NH2)2, C4H9Si(CH3)(NH2)2, (C4H9)2Si(NH2)2, C5H<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2, C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2, C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2, C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2, C9H<h2 style=";text-align:left;direction:ltr"> 19 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 21 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 23 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 25 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 27 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 14 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 29 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 31 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 16 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 33 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 35 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2、C<h2 style=";text-align:left;direction:ltr"> 18 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 37 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(NH2)2, (CH3)3SiNH2, C2H5Si(CH3)2NH2, (C2H5)2Si(CH3)NH2, (C2H5)3SiNH2, C3H7Si(CH3)2NH2, (C3H7)2Si(CH3)NH2, (C3H7)3SiNH2, C4H9Si(CH3)2NH2, (C4H9)3SiNH2, C5H<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2, C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2, C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2, C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2, C9H<h2 style=";text-align:left;direction:ltr"> 19 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 21 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 23 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 25 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 27 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 14 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 29 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 31 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 16 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 33 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 35 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、C<h2 style=";text-align:left;direction:ltr"> 18 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 37 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2NH2、(CH3)2Si(H)NH2、CH3Si(H)2NH2、(C2H5)2Si(H)NH2、C2H5Si(H)2NH2、C2H5Si(CH3)(H)NH2、(C3H7)2Si( H)NH2、C3H7Si(H)2NH2、CF3CH2CH2Si(NH2)3、C2F5CH2CH2Si(NH2)3、C3F7CH2CH2CH2Si(NH2)3、C4F9CH2CH2Si(NH2)3、C5F<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(NH2)3, C6F<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(NH2)3, C7F<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(NH2)3, C8F<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(NH2)3, CF3CH2CH2Si(CH3)(NH2)2, C2F5CH2CH2Si(CH3)(NH2)2, C3F7CH2CH2Si(CH3)(NH2)2, C4F9CH2CH2Si(CH3)(NH2)2, C5F<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(CH3)(NH2)2, C6F<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(CH3)(NH2)2, C7F<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(CH3)(NH2)2, C8F<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(CH3)(NH2)2, CF3CH2CH2Si(CH3)2NH2, C2F5CH2CH2Si(CH3)2NH2, C3F7CH2CH2Si(CH3)2NH2, C4F9CH2CH2Si(CH3)2NH2, C5F<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> CH2CH2Si(CH3)2NH2, C6F<h2 style=";text-align:left;direction:ltr"> 13CH2CH2Si(CH3)2NH2, C7F 15 CH2CH2Si(CH3)2NH2, C8F 17 Aminosilanes such as CH2CH2Si(CH3)2NH2, CF3CH2CH2Si(CH3)(H)NH2, aminodimethylvinylsilane, aminodimethylphenylethylsilane, aminodimethylphenylsilane, aminomethyldiphenylsilane, and aminodimethyl-t-butylsilane, or aminosilanes in which the amino group (-NH2 group) of the aminosilane is replaced with -N=C=O, dialkylamino groups (-N(CH3)2, -N(C2H5)2, etc.), t-butylamino groups, allylamino groups, -N=C=S, -N3, -NHC(=O)CH3, -NHC(=O)CF3, -N( CH3)C(=O)CH3, -N(CH3)C(=O)CF3, -N=C(CH3)OSi(CH3)3, -N=C(CF3)OSi(CH3)3, -NHC(=O)-OSi(CH3)3, -NHC(=O)-NH-Si(CH3)3 (e.g., N,N'-bis(trimethylsilyl)urea, etc.), imidazole ring (e.g., N-trimethylsilylimidazole, etc.), triazole ring (e.g., N-trimethylsilyltriazole, etc.), tetrazole ring, oxazolidinone ring, morpholine ring, -NH-C(=O)-Si(CH3)3, -N(S(=O)2R 4 )2(where R 4 are each independently selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and a fluorine atom. For example, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide, etc.), and a substituent having a structure of the following general formula [1-2]: [ka] (In the above general formula [1-2], R 5 are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms. For example, N-(trimethylsilyl)N,N-difluoromethane-1,3-bis(sulfonyl)imide, -N=C(NR 6 2)2, -N=C(NR 62)R 6 (where R 6 are each independently selected from a hydrogen group, a -C≡N group, a -NO2 group, and a hydrocarbon group in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and the hydrocarbon group may have oxygen atoms and / or nitrogen atoms. For example, 2-trimethylsilyl-1,1,3,3-tetramethylguanidine, -N(R a1 )R a2 (Here, the above R a1 represents a hydrogen atom or a saturated or unsaturated alkyl group, and R a2 represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a saturated or unsaturated heterocycloalkyl group. a1 and R a2 may be bonded to each other to form a saturated or unsaturated heterocycloalkyl group having a nitrogen atom. a3 )-Si(R a4 )(R a5 )(R a6 ) (where, the above R a3 represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a trimethylsilyl group, or a dimethylsilyl group, and the R a4 , R a5 and R a6 each independently represents a hydrogen atom or an organic group, R a4 , R a5 and R a6is at least 1. For example, -N(R) is a methyl group, and -N(R) is a methyl group. a7 )-C(=O)R a8 (Here, the above R a7 represents a hydrogen atom, a methyl group, a trimethylsilyl group, or a dimethylsilyl group, and R a8 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group, or a trialkylsilylamino group. Examples include N-trimethylsilylacetamide, N-trimethylsilyltrifluoroacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bis(trimethylsilyl)acetamide, bis(trimethylsilyl)trifluoroacetamide, etc.

[0066] As a silylating agent in which X in the above general formula [1] is a monovalent organic group in which the element bonded to the Si element is oxygen, for example, a silylating agent in which the amino group (-NH2 group) of the above aminosilane is bonded to -OC(=A)R a9 (Here, A above is O, CHR a10 , CHOR a10 , C.R. a10 R a10 , or NR a11 indicates R a9 , R a10each independently represents a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a fluorine-containing alkyl group, a chlorine-containing alkyl group, a trialkylsilyl group, a trialkylsiloxy group, an alkoxy group, a phenyl group, a phenylethyl group, or an acetyl group, and a11 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group. Examples include trimethylsilyl acetate, dimethylsilyl acetate, monomethylsilyl acetate, trimethylsilyl trifluoroacetate, dimethylsilyl trifluoroacetate, monomethylsilyl trifluoroacetate, trimethylsilyl trichloroacetate, trimethylsilyl propionate, and trimethylsilyl butyrate. a12 )=N(R a13 ) (where, the above R a12 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group, or a trialkylsilylamino group, and R a13 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group. a14 )=CH-C(=O)R a15 (Here, the above R a14 and R a15 each independently represents a hydrogen atom or an organic group. For example, trimethylsilyloxy-3-penten-2-one, 2-trimethylsiloxypent-2-en-4-one, etc.), -OR a16 (Here, the above R a16 represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a fluorine-containing alkyl group. For example, CH3Si(OCH3)3, C2H5Si(OCH3)3, C3H7Si(OCH3)3, C4H9Si(OCH3)3, C5H 11 Si(OCH3)3, C6H 13 Si(OCH3)3, C7H 15 Si(OCH3)3, C8H 17 Si(OCH3)3, C9H 19 Si(OCH3)3, C 10 H 21 Si(OCH3)3, C 11 H 23 Si(OCH3)3, C 12 H25 Si(OCH3)3、C 13 H 27 Si(OCH3)3、C 14 H 29 Si(OCH3)3、C 15 H 31 Si(OCH3)3、C 16 H 33 Si(OCH3)3、C 17 H 35 Si(OCH3)3、C 18 H 37 Si(OCH3)3、(CH3)2Si(OCH3)2、C2H5Si(CH3)(OCH3)2、(C2H5)2Si(OCH3)2、C3H7Si (CH3)(OCH3)2、(C3H7)2Si(OCH3)2、C4H9Si(CH3)(OCH3)2、(C4H9)2Si(OCH3)2、C5H 11 Si(CH3)(OCH3)2、C6H 13 Si(CH3)(OCH3)2、C7H 15 Si(CH3)(OCH3)2、C8H 17 Si(CH3)(OCH3)2、C9H 19 Si(CH3)(OCH3)2、C 10 H 21 Si(CH3)(OCH3)2、C 11 H 23 Si(CH3)(OCH3)2、C 12 H 25 Si(CH3)(OCH3)2、C 13 H 27 Si(CH3)(OCH3)2、C 14 H 29 Si(CH3)(OCH3)2、C 15 H 31 Si(CH3)(OCH3)2、C 16 H 33 Si(CH3)(OCH3)2、C 17 H 35 Si(CH3)(OCH3)2、C 18 H 37Si(CH3)(OCH3)2, (CH3)3SiOCH3, C2H5Si(CH3)2OCH3, (C2H5)2Si(CH3)OCH3, (C2H5)3SiOCH3, C3H7Si(CH3)2OCH3, (C3H7)2Si(CH3)OCH3, (C3H7)3SiOCH3, C4H9Si(CH3)2OCH3, (C4H9)3SiOCH3, C5H 11 Si(CH3)2OCH3, C6H 13 Si(CH3)2OCH3, C7H 15 Si(CH3)2OCH3, C8H 17 Si(CH3)2OCH3, C9H 19 Si(CH3)2OCH3, C 10 H 21 Si(CH3)2OCH3, C 11 H 23 Si(CH3)2OCH3, C 12 H 25 Si(CH3)2OCH3, C 13 H 27 Si(CH3)2OCH3, C 14 H 29 Si(CH3)2OCH3, C 15 H 31 Si(CH3)2OCH3, C 16 H 33 Si(CH3)2OCH3, C 17 H 35 Si(CH3)2OCH3, C 18 H 37 Alkylmethoxysilanes such as Si(CH3)2OCH3, (CH3)2Si(H)OCH3, CH3Si(H)2OCH3, (C2H5)2Si(H)OCH3, C2H5Si(H)2OCH3, C2H5Si(CH3)(H)OCH3, (C3H7)2Si(H)OCH3, or CF3CH2CH2Si(OCH3)3, C2F5CH2CH2Si(OCH3)3, C3F7CH2CH2Si(OCH3)3, C4F9CH2CH2Si(OCH3)3, C5F 11 CH2CH2Si(OCH3)3, C6F 13 CH2CH2Si(OCH3)3, C7F 15 CH2CH2Si(OCH3)3, C8F 17CH2CH2Si(OCH3)3, CF3CH2CH2Si(CH3)(OCH3)2, C2F5CH2CH2Si(CH3)(OCH3)2, C3F7CH2CH2Si(CH3)(OCH3)2, C4F9CH2CH2Si(CH3)(OCH3)2, C5F 11 CH2CH2Si(CH3)(OCH3)2, CF 13 CH2CH2Si(CH3)(OCH3)2, C7F 15 CH2CH2Si(CH3)(OCH3)2, C8F 17 CH2CH2Si(CH3)(OCH3)2, CF3CH2CH2Si(CH3)2OCH3, C2F5CH2CH2Si(CH3)2OCH3, C3F7CH2CH2Si(CH3)2OCH3, C4F9CH2CH2Si(CH3)2OCH3, C5F 11 CH2CH2Si(CH3)2OCH3, C6F 13 CH2CH2Si(CH3)2OCH3, C7F 15 CH2CH2Si(CH3)2OCH3, C8 F 17 Fluoroalkylmethoxysilanes such as CH2CH2Si(CH3)2OCH3 and CF3CH2CH2Si(CH3)(H)OCH3, or compounds in which the methyl group moiety of the methoxy group of the above methoxysilane is replaced with a monovalent hydrocarbon group having 2 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced with fluorine atoms, etc.), -OS(=O)2-R a17 (where, the above R a17 represents an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group, a phenyl group, a tolyl group, or an -O-Si(CH3)3 group. Examples include those substituted with -OP(-O-Si(CH3)3)2 (e.g., trimethylsilyl sulfonate, trimethylsilyl benzene sulfonate, trimethylsilyl toluene sulfonate, trimethylsilyl trifluoromethane sulfonate, trimethylsilyl perfluorobutane sulfonate, bistrimethylsilyl sulfate, etc.) or -OP(-O-Si(CH3)3)2 (e.g., tristrimethylsilyl phosphite, etc.).

[0067] Furthermore, examples of silylating agents in which X in the above general formula [1] is a monovalent organic group in which the element bonded to the Si element is oxygen include hexamethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,1-triethyl-3,3-dimethyldisiloxane, 1,1,3,3-tetra-n-octyldimethyldisiloxane, bis(nonafluorohexyl)tetramethyldisiloxane, 1,3-bis(trifluoropropyl)tetramethyldisiloxane, and 1,3-di-n-butyltetramethyldisiloxane. Siloxane, 1,3-di-n-octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, hexa-n-butyldisiloxane, hexaethyldisiloxane, hexavinyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, vinylpentamethyldisiloxane, 1,3-bis(3-chloroisobutyl)tetramethyldisiloxane, hexaphenyldisiloxane, 1,1,1-triethyl-3,3,3-trimethyldisiloxane, 1,3-bis(chloromethyl)tetramethyldisiloxane Methyldisiloxane, 1,1,3,3-tetraphenyldimethyldisiloxane, pentamethyldisiloxane, 1,3-bis(3-chloropropyl)tetramethyldisiloxane, 1,3-dichloro-1,3-diphenyl-1,3-dimethyldisiloxane, n-butyl-1,1,3,3-tetramethyldisiloxane, 1,3-di-t-butyldisiloxane, vinyl-1,1,3,3-tetramethyldisiloxane, 1,1,1-trimethyl-3,3,3-triphenyldisiloxane, 3,3-diphenyltetramethyltrisiloxane, 3-phenylheptame Chiltrisiloxane, hexamethylcyclotrisiloxane, n-propylheptamethyltrisiloxane, 3-ethylheptamethyltrisiloxane, 3-(3,3,3-trifluoropropyl)heptamethyltrisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, octamethyltrisiloxane, 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane, hexaphenylcyclotrisiloxane, 1,1,1,5,5,5-hexamethyltrisiloxane, 3-phenyl-1,1,3,5,5-Pentamethyltrisiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 3-octylheptamethyltrisiloxane, 1,3,5-triphenyltrimethylcyclotrisiloxane, 1,1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,5,5,5-hexaethyl-3-methyltrisiloxane, furfuryloxytrisiloxane, tetrakis(dimethylsiloxy)silane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, diphenylsiloxane-dimethylsiloxane copolymer, 1,3-diphenyl-1,3-dimethyldisiloxane Examples of the siloxane compound include siloxane compounds such as methylsiloxane, octamethylcyclotetrasiloxane, 1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane, tetra-n-propyltetramethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, decamethyltetrasiloxane, dodecamethylcyclohexasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexaphenylcyclotrisiloxane, polydimethylsiloxane, polyoctadecylmethylsiloxane, decamethylcyclopentasiloxane, poly(3,3,3-trifluoropropylmethylsiloxane), trimethylsiloxy-terminated polydimethylsiloxane, and 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane.

[0068] As a silylating agent in which X in the above general formula [1] is a monovalent organic group in which the element bonded to the Si element is carbon, for example, a silylating agent in which the amino group (-NH2 group) of the above aminosilane is converted into -C(S(=O)2R 7 )3(where R 7 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms. Examples include those in which hydrogen atoms are replaced by (trimethylsilyl)tris(trifluoromethanesulfonyl)methide, etc.

[0069] Furthermore, examples of the silylating agent in which X in the above general formula [1] is a monovalent organic group in which the element bonded to the Si element is a halogen include the above-mentioned aminosilanes in which the amino group (-NH group) is replaced with a chloro group, a bromo group, or an iodo group (e.g., chlorotrimethylsilane, bromotrimethylsilane, etc.).

[0070] The silylating agent may include a cyclic silazane compound. Examples of the cyclic silazane compound include cyclic disilazane compounds such as 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane and 2,2,6,6-tetramethyl-2,6-disila-1-azacyclohexane; cyclic trisilazane compounds such as 2,2,4,4,6,6-hexamethylcyclotrisilazane and 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane; and cyclic tetrasilazane compounds such as 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane.

[0071] The surface treatment agent composition may contain, in addition to the silylating agent, one or more catalysts for the silylating agent selected from the group consisting of Compound A (described below), acid imides, nitrogen-containing compounds, silicon-free nitrogen-containing heterocyclic compounds, and silylated heterocyclic compounds. Here, the catalyst promotes the reaction between the main surface and the silylating agent or enhances the liquid repellency of the surface treatment agent layer formed, and the catalyst itself or a modified product thereof may constitute a part of the surface treatment agent layer.

[0072] The concentration of the catalyst may be, for example, 0.005% by mass or more and 20% by mass or less, or 0.05% by mass or more and 15% by mass or less, relative to 100% by mass of the surface treatment agent composition.

[0073] Specific examples of the compound A include trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, and decyldimethylsilyl trifluoromethanesulfonate, and the compound A may contain one or more compounds selected from the above.These compounds may be used alone or in combination of two or more. Although the above-mentioned compound A may correspond to the above-mentioned silylating agent, when it is used as a catalyst, it means that it is used in combination with a silylating agent other than compound A.

[0074] The compound A may be obtained by reacting a silicon compound represented by the following general formula [2] with one or more acetic acids or sulfonic acids selected from the group consisting of trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride. The excess silicon compound represented by the following general formula [2] remaining without being consumed in this reaction can be used as the silylating agent together with the compound A obtained in the reaction. The silicon compound represented by the following general formula [2] may be reacted, for example, in a molar ratio of 0.2 to 100,000 times, preferably 0.5 to 50,000 times, more preferably 1 to 10,000 times, the acetic acid or sulfonic acid.

[0075] R 2 c (H) d Si-X [2]

[0076] In the above general formula [2], R 2 c (H) dExamples of Si- include (CH3)3Si-, (CH3)2(H)Si-, (C4H9)(CH3)2Si-, and (C6H 13 )(CH3)2Si-, (C8H 17 )(CH3)2Si-, (C 10 H 21 )(CH3)2Si-, etc. X is the same as in the general formula [1] above.

[0077] Furthermore, the compound A may be at least one selected from the group consisting of sulfonic acids represented by the following general formula [3], anhydrides of the sulfonic acids, salts of the sulfonic acids, and sulfonic acid derivatives represented by the following general formula [4]: R 8 -S(=O)2OH [3] [In the above general formula [3], R 8 is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and hydroxyl groups.] R 8' -S(=O)2O-Si(H) 3-r (R 9 ) r [4] [In the above general formula [4], R 8' is a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R 9 are each independently at least one group selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and r is an integer of 1 to 3.

[0078] Furthermore, the compound A may be at least one selected from the group consisting of sulfonate esters represented by the following general formula [5], sulfonimides represented by the following general formulas [6] and [7], sulfonimide derivatives represented by the following general formulas [8] and [9], sulfonmethides represented by the following general formula

[10] , and sulfonmethide derivatives represented by the following general formula

[11] . R 10 -S(=O)2OR 11 [5] [In the above general formula [5], R 10 is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R 11 is a monovalent alkyl group having 1 to 18 carbon atoms.] (R 12 -S(=O)2)2NH [6] [In the above general formula [6], R 12 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms.] [ka] [In the above general formula [7], R 13 is a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms.] ((R 14 -S(=O)2)2N) s Si(H) t (R 15 ) 4-s-t [8] [In the above general formula [8], R 14 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R 15 are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, s is an integer of 1 to 3, t is an integer of 0 to 2, and the sum of s and t is 3 or less. [ka] [In the above general formula [9], R 16 are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R 17are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, u is an integer of 1 to 3, v is an integer of 0 to 2, and the sum of u and v is 3 or less. (R 18 -S(=O)2)3CH

[10] [In the above general formula

[10] , R 18 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms.] ((R 19 -S(=O)2)3C) w Si(H) x (R 20 ) 4-w-x

[11] [In the above general formula

[11] , R 19 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R 20 are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, w is an integer of 1 to 3, x is an integer of 0 to 2, and the sum of w and x is 3 or less.

[0079] Examples of the acid imide compounds include compounds having a chemical structure in which an acid such as a carboxylic acid or phosphoric acid is imidized.

[0080] The nitrogen-containing compound may be at least one of the compounds represented by the following general formulas

[12] and

[13] . R 21 -N=C(NR 22 2)2

[12] R 21 -N=C(NR 22 2)R 22

[13] [In the above general formulas

[12] and

[13] , R 21is selected from a hydrogen group, a -C≡N group, a -NO2 group, an alkylsilyl group, and a hydrocarbon group in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and the hydrocarbon group may contain oxygen atoms and / or nitrogen atoms, but when it contains a nitrogen atom, it is considered to have a non-cyclic structure. 22 are each independently selected from a hydrogen group, a -C≡N group, a -NO2 group, and a hydrocarbon group in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and the hydrocarbon group may contain oxygen atoms and / or nitrogen atoms, but when it contains a nitrogen atom, it is considered to have a non-cyclic structure. Examples of the nitrogen-containing compound include guanidine, 1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, 1,3-diphenylguanidine, 1,2,3-triphenylguanidine, N,N'-diphenylformamidine, and 2,2,3,3,3-pentafluoropropylamidine.

[0081] The silicon-free nitrogen-containing heterocyclic compound and silylated heterocyclic compound may include at least one of the compounds represented by the following general formulas

[14] and

[15] . [ka] [In the above general formula

[14] , R 23 and R 24 are each independently a divalent organic group consisting of a carbon element and / or a nitrogen element and a hydrogen element, and the total number of carbon atoms and nitrogen atoms is 1 to 9, and when there are 2 or more carbon atoms, there may be carbon atoms that do not constitute a ring.] [ka] [In the above general formula

[15] , R 25is an alkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, a trialkylsilyl group having an alkyl group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, an alkenyl group having 2 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, an alkoxy group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, an amino group, an alkylamino group having an alkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, an aminoalkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, a nitro group, a cyano group, a phenyl group, a benzyl group, or a halogen group; 26 , R 27 and R 28 are each independently an alkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, or a hydrogen group.]

[0082] The silicon-free nitrogen-containing heterocyclic compound may contain heteroatoms other than nitrogen atoms, such as oxygen atoms and sulfur atoms, in the ring, may be aromatic, and may be a compound in which two or more rings are linked by a single bond or a divalent or higher polyvalent linking group. The compound may also have a substituent. Examples of the nitrogen-containing heterocyclic compound not containing a silicon atom include pyridine, pyridazine, pyrazine, pyrimidine, triazine, tetrazine, pyrrole, pyrazole, imidazole, triazole, tetrazole, oxazole, isoxazole, thiazole, isothiazole, oxadiazole, thiadiazole, quinoline, isoquinoline, cinnoline, phthalazine, quinoxaline, quinazoline, indole, indazole, benzimidazole, benzotriazole, benzoxazole, benzisoxazole, benzothiazole, benzisothiazole, benzoxadiazole, benzothiadiazole, saccharin, pyrrolidine, and piperidine.

[0083] Examples of the silylated heterocyclic compound include a silylated imidazole compound and a silylated triazole compound. Examples of the silylated heterocyclic compound include monomethylsilylimidazole, dimethylsilylimidazole, trimethylsilylimidazole, monomethylsilyltriazole, dimethylsilyltriazole, and trimethylsilyltriazole. Some of the above-mentioned silylated heterocyclic compounds fall under the category of the above-mentioned silylating agents, but when used as a catalyst, this means that they are used in combination with other silylating agents other than the silylated heterocyclic compounds.

[0084] In the surface treatment agent composition, the concentration of the silylating agent, or the total concentration of the silylating agent and the catalyst, relative to 100% by mass of the surface treatment agent composition, may be, for example, 0.01% by mass to 100% by mass, preferably 0.1% by mass to 50% by mass, and more preferably 0.5% by mass to 30% by mass.

[0085] The surface treatment agent composition may contain a solvent.

[0086] The solvent is not particularly limited as long as it dissolves the silylating agent. Examples of the solvent include organic solvents such as hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, alcohols, carbonate-based solvents, polyhydric alcohol derivatives, nitrogen-containing solvents, silicone solvents, and thiols. Among these, hydrocarbons, esters, ethers, halogen-containing solvents, sulfoxide-based solvents, and polyhydric alcohol derivatives that do not have an OH group are preferred. These may be used alone or in combination of two or more.

[0087] Examples of the hydrocarbons include linear, branched, or cyclic hydrocarbon solvents, aromatic hydrocarbon solvents, and terpene solvents, such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, and n-eicosane, as well as branched hydrocarbons corresponding to the carbon numbers thereof (e.g., isododecane, isocetane, etc.), cyclohexane, methylcyclohexane, and the like. Examples of solvents include cyclohexane, decalin, benzene, toluene, xylene, (ortho-, meta-, or para-)diethylbenzene, 1,3,5-trimethylbenzene, naphthalene, mesitylene, p-menthane, o-menthane, m-menthane, diphenylmenthane, limonene, α-terpinene, β-terpinene, γ-terpinene, bornane, norbornane, pinane, α-pinene, β-pinene, carane, longifolene, abietane, and terpene solvents.

[0088] Examples of the esters include ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl n-octanoate, methyl decanoate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, dimethyl adipate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl ethoxyacetate.

[0089] Furthermore, the esters may be cyclic esters such as lactone compounds. Examples of lactone compounds include β-propiolactone, γ-butyrolactone, γ-valerolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-nonanolactone, γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, and ε-hexanolactone.

[0090] Examples of the ethers include di-n-propyl ether, ethyl-n-butyl ether, di-n-butyl ether, ethyl-n-amyl ether, di-n-amyl ether, ethyl-n-hexyl ether, di-n-hexyl ether, di-n-octyl ether, as well as ethers having a branched hydrocarbon group such as diisopropyl ether and diisoamyl ether corresponding to the carbon numbers of these ethers, dimethyl ether, diethyl ether, methyl ethyl ether, methylcyclopentyl ether, diphenyl ether, tetrahydrofuran, and dioxane.

[0091] Examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, cyclohexanone, and isophorone.

[0092] Examples of the halogen element-containing solvent include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, and hexafluorobenzene; hydrofluorocarbons such as 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, and Zeorola H (manufactured by Zeon Corporation); methyl perfluoropropyl ether, methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, methyl perfluorohexyl ether, ethyl perfluorohexyl ether, Asahiklin AE-3000 (manufactured by Asahi Glass Co., Ltd.), Novec HFE-7100, Novec Examples include hydrofluoroethers such as HFE-7200, Novec7300, and Novec7600 (all manufactured by 3M), chlorocarbons such as tetrachloromethane, hydrochlorocarbons such as chloroform, chlorofluorocarbons such as dichlorodifluoromethane, hydrochlorofluorocarbons such as 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, and 1,2-dichloro-3,3,3-trifluoropropene, perfluoroethers, and perfluoropolyethers.

[0093] Examples of the sulfoxide solvent include dimethyl sulfoxide.

[0094] Examples of the carbonate solvent include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate.

[0095] Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2- Examples include methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, benzyl alcohol, 1-octanol, isooctanol, 2-ethyl-1-hexanol, and 4-methyl-2-pentanol.

[0096] Examples of derivatives of the above polyhydric alcohols that do not have an OH group include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, and triethylene glycol monoethyl ether acetate. acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methylpropyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate,Dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, glycerin triacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, etc.

[0097] Examples of the nitrogen-containing solvent include formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, diethylamine, triethylamine, and pyridine.

[0098] Examples of the silicone solvent include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane.

[0099] Examples of the thiols include 1-hexanethiol, 2-methyl-1-pentanethiol, 3-methyl-1-pentanethiol, 4-methyl-1-pentanethiol, 2,2-dimethyl-1-butanethiol, 3,3-dimethyl-1-butanethiol, 2-ethyl-1-butanethiol, 1-heptanethiol, benzylthiol, 1-octanethiol, 2-ethyl-1-hexanethiol, 1-nonanethiol, 1-decanethiol, 1-undecanethiol, 1-dodecanethiol, and 1-tridecanethiol.

[0100] The solvent preferably contains an aprotic solvent. The content of the aprotic solvent is, for example, 80% by mass or more, preferably 90% by mass or more, relative to 100% by mass of the solvent. It is more preferable that the solvent is an aprotic solvent, i.e., the solvent contains an aprotic solvent at a content of 100% by mass relative to 100% by mass of the solvent.

[0101] Aprotic solvents include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxides, carbonate solvents, polyhydric alcohol derivatives, nitrogen-containing solvents, silicone solvents, etc. These may be used alone or in combination of two or more. Among these, it is preferable to use one or more selected from the group consisting of derivatives of polyhydric alcohols, hydrocarbons, and ethers.

[0102] From the viewpoint of cost and solubility, derivatives of polyhydric alcohols (which do not have an OH group in the molecule) are preferred, such as diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol dimethyl ether, 3-methoxy-3-methyl-1-butyl acetate, Preferred are propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, and dipropylene glycol diacetate. Also preferred are propylene carbonate, linear or branched hydrocarbon solvents having 6 to 12 carbon atoms, p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, and pinane.

[0103] Examples of surface treatment agent compositions containing a silylating agent and a solvent include those in which the silylating agent is hexamethyldisilazane, heptamethyldisilazane, N-(trimethylsilyl)dimethylamine, bis(dimethylamino)dimethylsilane, bis(trimethylsilyl)trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-trimethylsilylimidazole, trimethylsilyltriazole, bistrimethylsilyl sulfate, 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane, 2,2,4,4,6,6-hexamethyldisilazane, The catalyst may contain one or more selected from the group consisting of trimethylsilylcyclotrisilazane, hexamethyldisiloxane, trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, trimethylsilylbenzenesulfonate, and trimethylsilyl toluenesulfonate, and the solvent may contain one or more selected from the group consisting of propylene carbonate, linear hydrocarbon solvents having 7 to 10 carbon atoms, menthane, pinane, γ-butyrolactone, propylene glycol monomethyl ether acetate, and 3-methoxy-3-methyl-1-butyl acetate.

[0104] The surface treatment agent composition may contain no water or may contain water in an amount of 2% by mass or less relative to 100% by mass of the surface treatment agent composition. In this way, it is possible to use a surface treatment agent composition that is substantially free of water.

[0105] The surface treatment agent composition may contain other components in addition to the above-mentioned components, provided that the object of the present invention is not impaired. Examples of such other components include oxidizing agents such as hydrogen peroxide and ozone, surfactants, and antioxidants such as BHT.

[0106] The surface treatment agent composition of this embodiment is obtained by mixing the above-mentioned components. The obtained mixture may be purified using an adsorbent, a filter, or the like, as necessary. Alternatively, each component may be purified in advance by distillation, or may be purified using an adsorbent, a filter, or the like.

[0107] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. Below, examples of reference forms are given. 1. A method for processing a main surface of a semiconductor substrate having a pattern-formed region on the main surface of the substrate, in which a pattern having a relief structure with a pattern dimension of 30 nm or less is formed, and a pattern-non-formed region in which the pattern is not formed, comprising: a surface treatment step of contacting the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate with a surface treatment agent composition containing a silylating agent, On the surface of the pattern non-forming region after the surface treatment step, The contact angle of IPA with 2-propanol is 2° or more at room temperature (25°C), and / or The water contact angle with pure water is 50° or more at room temperature of 25°. Processing method. 2. The processing method according to 1., A processing method, wherein the pattern dimension is at least one width dimension in an in-plane direction of the main surface and / or at least one height dimension in a direction perpendicular to the main surface. 3. The processing method according to 1. or 2., the surface treatment step is to form a surface treatment agent layer on the entire main surface of the semiconductor substrate, On the surface of the surface treatment agent layer The IPA contact angle is 2° or more at room temperature (25°C), and / or The water contact angle is 55° or more at room temperature of 25°. Processing method. 4. The processing method according to any one of 1. to 3., A treatment method, wherein the uneven structure contains one or more selected from the group consisting of Si, Ti, Ge, W, and Ru, and oxides, nitrides, nitrogen oxides, carbonitrides, and carbonoxides containing one or more of these elements. 5. The processing method according to any one of 1. to 4., The treatment method, wherein the surface treatment agent composition contains a solvent. 6. The processing method according to 5., The method of processing, wherein the solvent comprises an aprotic solvent. 7. The processing method according to 6., A processing method in which the solvent contains the aprotic solvent in an amount of 100 mass % relative to 100 mass % of the solvent. 8. The processing method according to 6. or 7., The treatment method, wherein the aprotic solvent comprises one or more selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxides, carbonate solvents, derivatives of polyhydric alcohols, nitrogen-containing solvents, and silicone solvents. 9. The processing method according to any one of 6. to 8., The process wherein the solvent comprises a carbonate solvent or a lactone. 10. The processing method according to any one of 6. to 8., The process, wherein the solvent comprises propylene carbonate or gamma-butyrolactone. 11. The processing method according to any one of 6. to 8., The treatment method, wherein the solvent comprises one or more selected from the group consisting of derivatives of polyhydric alcohols, hydrocarbons, and ethers. 12. The processing method according to any one of 1. to 11., The treatment method, wherein the silylating agent contains a silicon compound represented by the following general formula [1]: R 1 a Si(H) b X 4-a-b [1] (In the above general formula [1], R 1 are each independently an organic group containing a hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and X are each independently a monovalent functional group in which the element bonded to the Si atom is nitrogen, oxygen, carbon, or halogen, a is an integer of 1 to 3, b is an integer of 0 to 2, and the sum of a and b is 1 to 3. 13. The processing method according to any one of 1. to 12., The method of the present invention, wherein the silylating agent has a trialkylsilyl group. 14. The processing method according to any one of 1. to 13., The treatment method, wherein the element that bonds to the Si element in the silylating agent is nitrogen. 15. The processing method according to any one of 1. to 14., The treatment method, wherein the content of the silylating agent is 0.1% by mass or more and 50% by mass or less, relative to 100% by mass of the surface treatment agent composition. 16. The processing method according to any one of 1. to 15., The treatment method, wherein the surface treatment agent composition contains a catalyst. 17. The method according to 16, further comprising: The catalyst is selected from the group consisting of trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, decyldimethylsilyl trifluoroacetate, A treatment method comprising one or more compounds selected from the group consisting of silyl trifluoromethanesulfonate, sulfonic acid represented by the following general formula [3], anhydrides of the sulfonic acid, salts of the sulfonic acid, sulfonic acid derivatives represented by the following general formula [4], sulfonic acid esters represented by the following general formula [5], sulfonimides represented by the following general formulas [6] and [7], sulfonimide derivatives represented by the following general formulas [8] and [9], sulfonmethides represented by the following general formula

[10] , sulfonmethide derivatives represented by the following general formula

[11] , acid imides, nitrogen-containing compounds, nitrogen-containing heterocyclic compounds, and silylated heterocyclic compounds. R 8 -S(=O) 2 OH [3] [In the above general formula [3], R 8 is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and hydroxyl groups.] R 8’ -S(=O) 2 O-Si(H) 3-r (R 9 ) r [4] [In the above general formula [4], R 8’ is a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R 9 are each independently at least one group selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and r is an integer of 1 to 3. R 10 -S(=O) 2 OR 11 [5] [In the above general formula [5], R 10 is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R 11 is a monovalent alkyl group having 1 to 18 carbon atoms.] (R 12 -S(=O) 2 ) 2 NH [6] [In the above general formula [6], R 12 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms.] TIFF0007727202000007.tif20153 [In the above general formula [7], R 13 is a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms.] ((R 14 -S(=O) 2 ) 2 N) s Si(H) t (R 15 ) 4-s-t [8] [In the above general formula [8], R 14 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R 15 are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, s is an integer of 1 to 3, t is an integer of 0 to 2, and the sum of s and t is 3 or less. TIFF0007727202000008.tif23153 [In the above general formula [9], R 16 are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R 17 are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, u is an integer of 1 to 3, v is an integer of 0 to 2, and the sum of u and v is 3 or less. (R 18 -S(=O) 2 ) 3 CH

[10] [In the above general formula

[10] , R 18 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms.] ((R 19 -S(=O) 2 ) 3 C) w Si(H) x (R 20 ) 4-w-x

[11] [In the above general formula

[11] , R 19 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R 20 are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, w is an integer of 1 to 3, x is an integer of 0 to 2, and the sum of w and x is 3 or less. 18. The processing method according to 16. or 17., The treatment method, wherein the content of the catalyst is 0.005% by mass or more and 20% by mass or less relative to 100% by mass of the surface treatment agent composition. 19. The processing method according to any one of 1. to 18., The treatment method, wherein the surface treatment agent composition does not contain water or contains water in an amount of 2 mass % or less relative to 100 mass % of the surface treatment agent composition. 20. The processing method according to any one of 1. to 19., The surface treatment method, wherein the surface treatment step is performed by contacting the surface treatment composition with the main surface using a spin coating method. 21. The processing method according to any one of 1. to 20., The method further comprises, prior to the surface treatment step, at least one cleaning step of contacting the main surface of the semiconductor substrate with an aqueous cleaning solution. 22. The method according to 21, further comprising: The treatment method, wherein the aqueous cleaning solution comprises one or more selected from the group consisting of water, alcohol, an aqueous ammonium hydroxide solution, an aqueous tetramethylammonium solution, an aqueous hydrochloric acid solution, an aqueous hydrogen peroxide solution, an aqueous sulfuric acid solution, and an organic solvent. 23. The processing method according to 21. or 22, The processing method includes, after the cleaning step and before the surface treatment step, a first rinsing step of contacting the main surface of the semiconductor substrate with a first rinsing solution. 24. The processing method according to any one of 1. to 23., The processing method further comprises, after the surface treatment step, a second rinsing step of contacting the main surface of the semiconductor substrate with a second rinsing solution. 25. The processing method according to any one of 1. to 24., The processing method further comprises, after the surface treatment step, a drying step of drying the main surface of the semiconductor substrate. 26. The processing method according to any one of 1. to 25., a removing step, after the surface treatment step, of removing from the main surface the surface treatment agent layer formed on the main surface of the semiconductor substrate by the surface treatment step. 27. A method for processing a main surface of a semiconductor substrate having a pattern-formed region on the main surface of the substrate, in which a pattern having a relief structure with a pattern dimension of 30 nm or less is formed, and a pattern-unformed region in which the pattern is not formed, comprising: a surface treatment step of contacting the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate with a surface treatment agent composition containing a silylating agent; and on the surface of the pattern non-forming region after the surface treatment step, The contact angle of IPA with 2-propanol is 2° or greater, and / or An evaluation process to determine whether the water contact angle with pure water is 50° or more A processing method comprising: 28. A surface treatment composition used to treat a principal surface of a semiconductor substrate having a pattern-formed region on the principal surface of the substrate, in which a pattern having a relief structure with a pattern dimension of 30 nm or less is formed, and a pattern-non-formed region in which the pattern is not formed, comprising: a silylating agent, The IPA contact angle, as determined by the following procedure, is 2° or greater, and / or The water contact angle, determined by the following procedure, is 50° or more. Surface treatment composition. (procedure) The surface treatment agent composition is brought into contact with the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate. After contacting the surface treatment agent composition, on the surface of the pattern non-forming region, The contact angle with 2-propanol was measured at room temperature of 25°C, and the measured value was taken as the IPA contact angle (°). The contact angle with pure water is measured at room temperature of 25°C, and the measured value is taken as the water contact angle (°). 29. The surface treatment composition according to 28, The surface treatment agent composition, wherein the silylating agent has a trialkylsilyl group. 30. The surface treatment composition according to 28. or 29., A surface treatment composition comprising a solvent. 31. The surface treatment composition according to 30, The surface treatment agent composition, wherein the solvent comprises an aprotic solvent. 32. The surface treatment composition according to 31, The surface treatment agent composition, wherein the aprotic solvent comprises one or more solvents selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxides, carbonate solvents, polyhydric alcohol derivatives, nitrogen-containing solvents, and silicone solvents. 33. The surface treatment agent composition according to any one of items 30 to 32, the silylating agent comprises one or more selected from the group consisting of hexamethyldisilazane, heptamethyldisilazane, N-(trimethylsilyl)dimethylamine, bis(dimethylamino)dimethylsilane, bis(trimethylsilyl)trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-trimethylsilylimidazole, trimethylsilyltriazole, bistrimethylsilyl sulfate, 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, hexamethyldisiloxane, trimethylsilyltrifluoroacetate, trimethylsilyltrifluoromethanesulfonate, trimethylsilylbenzenesulfonate, and trimethylsilyltoluenesulfonate; The surface treatment agent composition, wherein the solvent comprises one or more selected from the group consisting of propylene carbonate, linear hydrocarbon solvents having 7 to 10 carbon atoms, menthane, pinane, γ-butyrolactone, propylene glycol monomethyl ether acetate, and 3-methoxy-3-methyl-1-butyl acetate. 34. The surface treatment agent composition according to any one of items 28 to 33, The surface treatment agent composition comprises a catalyst. 35. The surface treatment composition according to 34, The catalyst is selected from the group consisting of trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, decyldimethylsilyl a surface treatment agent composition comprising one or more compounds selected from the group consisting of methyltrifluoromethanesulfonate, a sulfonic acid represented by the following general formula [3], an anhydride of the sulfonic acid, a salt of the sulfonic acid, a sulfonic acid derivative represented by the following general formula [4], a sulfonic acid ester represented by the following general formula [5], a sulfonimide represented by the following general formulas [6] and [7], a sulfonimide derivative represented by the following general formulas [8] and [9], a sulfonmethide represented by the following general formula

[10] , a sulfonmethide derivative represented by the following general formula

[11] , an acid imide, a nitrogen-containing compound, a nitrogen-containing heterocyclic compound, and a silylated heterocyclic compound. R 8 -S(=O) 2 OH [3] [In the above general formula [3], R 8 is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and hydroxyl groups.] R 8’ -S(=O) 2 O-Si(H) 3-r (R 9 ) r [4] [In the above general formula [4], R 8’ is a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R 9 are each independently at least one group selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and r is an integer of 1 to 3. R 10 -S(=O) 2 OR 11 [5] [In the above general formula [5], R 10 is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R 11 is a monovalent alkyl group having 1 to 18 carbon atoms.] (R 12 -S(=O) 2 ) 2 NH [6] [In the above general formula [6], R 12 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms.] TIFF0007727202000009.tif20153 [In the above general formula [7], R 13 is a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms.] ((R 14 -S(=O) 2 ) 2 N) s Si(H) t (R 15 ) 4-s-t [8] [In the above general formula [8], R 14 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R 15 are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, s is an integer of 1 to 3, t is an integer of 0 to 2, and the sum of s and t is 3 or less. TIFF0007727202000010.tif23153 [In the above general formula [9], R 16 are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R 17 are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, u is an integer of 1 to 3, v is an integer of 0 to 2, and the sum of u and v is 3 or less. (R 18 -S(=O) 2 ) 3 CH

[10] [In the above general formula

[10] , R 18 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms.] ((R 19 -S(=O) 2 ) 3 C) w Si(H) x (R 20 ) 4-w-x

[11] [In the above general formula

[11] , R 19 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R 20 are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, w is an integer of 1 to 3, x is an integer of 0 to 2, and the sum of w and x is 3 or less. [Example]

[0108] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the descriptions of these examples.

[0109] <Production of Surface Treatment Agent Composition> (Surface treatment composition 1) N-(trimethylsilyl)dimethylamine (TMSDMA) and propylene glycol monomethyl ether acetate (PGMEA) were mixed at a liquid temperature of 25°C and stirred for 1 minute to prepare surface treatment composition 1 containing 1 mass% TMSDMA as a silylation agent. For the surface treatment described below, surface treatment composition 1 was used within 30 minutes of its preparation. Hereinafter, "within 30 minutes of preparation" will be referred to as "immediately after preparation."

[0110] (Surface treatment composition 2) TMSDMA and PGMEA were mixed at a liquid temperature of 25°C and stirred for 1 minute. Trifluoroacetic acid (TFA) was then added and reacted with TMSDMA to prepare surface treatment composition 2 containing 0.1 mass% of trimethylsilyl trifluoroacetate (TMSTFA) as compound A and 1 mass% of TMSDMA as a silylating agent. Surface treatment composition 2 was used immediately after preparation for the surface treatment described below.

[0111] (Surface treatment composition 3) Surface treatment agent composition 3 was prepared in the same manner as surface treatment agent composition 2, except that TMSDMA was replaced with hexamethyldisilazane (HMDS). Surface treatment agent composition 3 was used immediately after preparation for the surface treatment described below.

[0112] (Surface treatment agent compositions 4 to 37) Surface treatment agent compositions 4 to 37 were prepared in the same manner as the above surface treatment agent compositions 1, 2, and 3, except that the raw materials listed in Table 1 were used. Surface treatment agent compositions 4 to 37 were used immediately after preparation for the surface treatment described below. The abbreviations in Table 1 and the corresponding compound names are shown in Table 2.

[0113] <Substrate manufacturing> First, a silicon substrate was prepared in which a convex structure having a plurality of approximately cylindrical convex portions with an aspect ratio of 22 in a cross-sectional view and a pattern width of 19 nm was formed on the surface at a pitch of 90 nm (the total distance between the width of the convex portion and the distance between adjacent convex portions), and in which a smooth area on the periphery of the convex structure was formed with no pattern formed. Hereinafter, the portion having the convex structure will be referred to as a "pattern-formed region," and the smooth portion where no pattern is formed will be referred to as a "pattern-non-formed region." The IPA contact angle and water contact angle described below were measured in the pattern-free region, and the area of ​​the pattern-free region per contact angle measurement point was approximately 250 mm 2 It was.

[0114] <Substrate surface treatment> The surface of the substrate was dry cleaned by UV / O3 irradiation. The surfaces of the pattern-forming region and non-pattern-forming region of the substrate were oxidized to silicon oxide. Next, the substrate was placed on a spin coater, and while rotating the substrate at a speed of 200 rpm, 2-propanol (IPA), the surface treatment agent composition shown in Table 1, and IPA were sprayed onto the substrate at a speed of 200 cc / min, in that order. Finally, the substrate was dried by spraying N2 onto the substrate.

[0115] In Comparative Example 1, the same treatment was carried out except that the above-mentioned surface treatment agent composition was not ejected.

[0116] [Table 1]

[0117] [Table 2]

[0118] <Evaluation> (IPA contact angle) At room temperature of 25°C, the surface-treated silicon substrate was set in a contact angle meter and placed on a horizontal table. Approximately 1 μL of 2-propanol (IPA) was dropped onto the non-patterned area, and the state of the droplet was observed after 5 seconds. The contact angle (°) of the IPA at this time was measured as the IPA contact angle. The IPA contact angles are shown in Table 3. (water contact angle) At room temperature of 25°C, the surface-treated silicon substrate was set in a contact angle meter using the same substrate as used in the above IPA contact angle measurement. With the substrate placed on a horizontal table, approximately 1 μL of pure water was dropped onto the non-patterned area. The state of the droplet was observed after 5 seconds, and the contact angle (°) of pure water at this time was measured as the water contact angle. The water contact angles are shown in Table 3. (Pattern failure rate) Furthermore, using the same substrate as used in the contact angle measurement, the pattern formation area was observed under an electron microscope (SEM, SU8010, manufactured by Hitachi High-Technologies Corporation) at a magnification such that 500 to 600 convex portions were within the field of view, and the number of convex portions where pattern collapse had occurred was counted. The ratio of convex portions where collapsed to all convex portions is shown in Table 3 as the pattern collapse rate (%).

[0119] [Table 3]

[0120] As described above, the surface treatment method according to the embodiments of the present disclosure is a more efficient method than the conventional method of separately evaluating a dummy smooth substrate to confirm whether a predetermined IPA contact angle and / or a predetermined water contact angle can be achieved.

[0121] Furthermore, as shown in Table 1, in Examples 1 to 37, which used surface treatment agent compositions 1 to 37, the pattern non-forming region of the substrate exhibited an IPA contact angle and a water contact angle equal to or greater than a predetermined value. Furthermore, as shown in Table 1, a significant portion of the convex portions in the pattern forming region of the substrate remained even after the cleaning or drying process, indicating that the pattern collapse rate could be reduced compared to Comparative Example 1.

[0122] This application claims priority based on Japanese Patent Application No. 2020-089194, filed on May 21, 2020, and Japanese Patent Application No. 2020-089201, filed on May 21, 2020, the disclosures of which are incorporated herein in their entireties. [Explanation of symbols]

[0123] 10 Substrate 12 Main Surfaces 14 Notch 16 Back side 20 Uneven structure 22 Convex part 24 recess 30 Pattern formation area 32 Non-patterned area 50 Bevel Area 51 Top Edge 52 Upper bevel 53 Front Shoulder 54 End face 55 Lower Bevel 60 Surface treatment composition 70 Surface treatment layer

Claims

1. 1. A processing method for processing a main surface of a semiconductor substrate having, on a main surface of the substrate, a pattern-formed region in which a pattern having a concavo-convex structure with a pattern dimension of 30 nm or less is formed, and a pattern-non-formed region in which the pattern is not formed, the method comprising: a surface treatment step of contacting the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate with a surface treatment agent composition that is a liquid containing a silylating agent and a solvent, On the surface of the pattern non-forming region after the surface treatment step, The contact angle of IPA with 2-propanol is 2° or more at room temperature (25°C), and / or The water contact angle with pure water is 50° or more at room temperature of 25°. Processing method.

2. 2. The processing method of claim 1, A processing method, wherein the pattern dimension is at least one width dimension in an in-plane direction of the main surface and / or at least one height dimension in a direction perpendicular to the main surface.

3. 3. The processing method according to claim 1 or 2, the surface treatment step is to form a surface treatment agent layer on the entire main surface of the semiconductor substrate, On the surface of the surface treatment agent layer The IPA contact angle is 2° or more at room temperature (25°C), and / or The water contact angle is 55° or more at room temperature of 25°. Processing method.

4. The processing method according to any one of claims 1 to 3, A treatment method, wherein the uneven structure contains one or more elements selected from the group consisting of Si, Ti, Ge, W, and Ru, and oxides, nitrides, nitrogen oxides, carbonitrides, and carbonoxides containing one or more of these elements.

5. The processing method according to any one of claims 1 to 4, The method of processing, wherein the solvent comprises an aprotic solvent.

6. 6. The processing method according to claim 5, The processing method, wherein the solvent contains the aprotic solvent in an amount of 100 mass % relative to 100 mass % of the solvent.

7. 7. The processing method according to claim 5 or 6, The treatment method, wherein the aprotic solvent comprises one or more selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxides, carbonate solvents, polyhydric alcohol derivatives, nitrogen-containing solvents, and silicone solvents.

8. The processing method according to any one of claims 5 to 7, The process wherein the solvent comprises a carbonate solvent or a lactone.

9. The processing method according to any one of claims 5 to 7, The processing method, wherein the solvent comprises propylene carbonate or gamma-butyrolactone.

10. The processing method according to any one of claims 5 to 7, The treatment method, wherein the solvent comprises one or more selected from the group consisting of derivatives of polyhydric alcohols, hydrocarbons, and ethers.

11. The processing method according to any one of claims 1 to 10, The treatment method, wherein the silylating agent contains a silicon compound represented by the following general formula [1]: R １ ａ Si (H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １ are each independently an organic group containing a hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and each X is independently a monovalent functional group in which the element bonded to the Si atom is nitrogen, oxygen, carbon, or halogen, a is an integer of 1 to 3, b is an integer of 0 to 2, and the sum of a and b is 1 to 3.

12. The processing method according to any one of claims 1 to 11, The method of the present invention, wherein the silylating agent has a trialkylsilyl group.

13. The processing method according to any one of claims 1 to 12, The treatment method, wherein the element that bonds to the Si element in the silylating agent is nitrogen.

14. The processing method according to any one of claims 1 to 13, The treatment method, wherein the content of the silylating agent is 0.1% by mass or more and 50% by mass or less, relative to 100% by mass of the surface treatment agent composition.

15. The processing method according to any one of claims 1 to 14, The treatment method, wherein the surface treatment agent composition contains a catalyst.

16. 16. The processing method of claim 15, The catalyst is selected from the group consisting of trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, decyldimethylsilyl trifluoroacetate, A treatment method comprising one or more compounds selected from the group consisting of silyl trifluoromethanesulfonate, a sulfonic acid represented by the following general formula [3], an anhydride of the sulfonic acid, a salt of the sulfonic acid, a sulfonic acid derivative represented by the following general formula [4], a sulfonic acid ester represented by the following general formula [5], a sulfonimide represented by the following general formulas [6] and [7], a sulfonimide derivative represented by the following general formulas [8] and [9], a sulfonmethide represented by the following general formula [10], a sulfonmethide derivative represented by the following general formula [11], an acid imide, a nitrogen-containing compound, a nitrogen-containing heterocyclic compound, and a silylated heterocyclic compound. R ８ -S(=O) ２ OH [3] [In the above general formula [3], R ８ is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and hydroxyl groups. R ８’ -S (=O) ２ O-Si (H) ３－ｒ (R) ９ ) ｒ [4] [In the above general formula [4], R ８’ is a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R ９ are each independently at least one group selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and r is an integer of 1 to 3. R １０ -S(=O) ２ OR １１ [5] [In the above general formula [5], R １０ is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R １１ is a monovalent alkyl group having 1 to 18 carbon atoms. (R １２ -S(=O) ２ ) ２ NH [6] [In the above general formula [6], R １２ are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and elemental fluorine. 【Chemical 1】 [In the above general formula [7], R １３ is a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms. (R １４ -S (=O) ２ ) ２ N) ｓ Si (H) ｔ (R) １５ ) ４－ｓ－ｔ [8] [In the above general formula [8], R １４ are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R １５ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, s is an integer of 1 to 3, t is an integer of 0 to 2, and the sum of s and t is 3 or less. 【Chemistry 2】 [In the above general formula [9], R １６ are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R １７ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, u is an integer of 1 to 3, v is an integer of 0 to 2, and the sum of u and v is 3 or less. (R １８ -S(=O) ２ ) ３ CH [10] [In the above general formula [10], R １８ are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and elemental fluorine. (R １９ -S (=O) ２ ) ３ C) ｗ Si (H) ｘ (R) ２０ ) ４－ｗ－ｘ [11] [In the above general formula [11], R １９ are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R ２０ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, w is an integer of 1 to 3, x is an integer of 0 to 2, and the sum of w and x is 3 or less.

17. 17. The method of claim 15 or 16, The treatment method, wherein the content of the catalyst is 0.005% by mass or more and 20% by mass or less relative to 100% by mass of the surface treatment agent composition.

18. The processing method according to any one of claims 1 to 17, The treatment method, wherein the surface treatment agent composition does not contain water or contains water in an amount of 2 mass% or less relative to 100 mass% of the surface treatment agent composition.

19. The method according to any one of claims 1 to 18, The surface treatment method, wherein the surface treatment step is performed by contacting the surface treatment composition with the main surface using a spin coating method.

20. The processing method according to any one of claims 1 to 19, The method further comprises, prior to the surface treatment step, at least one cleaning step of contacting the main surface of the semiconductor substrate with an aqueous cleaning solution.

21. 21. The processing method of claim 20, The treatment method, wherein the aqueous cleaning solution comprises one or more selected from the group consisting of water, alcohol, an aqueous ammonium hydroxide solution, an aqueous tetramethylammonium solution, an aqueous hydrochloric acid solution, an aqueous hydrogen peroxide solution, an aqueous sulfuric acid solution, and an organic solvent.

22. 22. The method of claim 20 or 21, The processing method includes, after the cleaning step and before the surface treatment step, a first rinsing step of contacting the main surface of the semiconductor substrate with a first rinsing solution.

23. The method according to any one of claims 1 to 22, The processing method further comprises, after the surface treatment step, a second rinsing step of contacting the main surface of the semiconductor substrate with a second rinsing solution.

24. The processing method according to any one of claims 1 to 23, The processing method further comprises, after the surface processing step, a drying step of drying the main surface of the semiconductor substrate.

25. The method according to any one of claims 1 to 24, a removing step, after the surface treatment step, of removing from the main surface the surface treatment agent layer formed on the main surface of the semiconductor substrate by the surface treatment step.

26. 1. A processing method for processing a main surface of a semiconductor substrate having, on a main surface of the substrate, a pattern-formed region in which a pattern having a concavo-convex structure with a pattern dimension of 30 nm or less is formed, and a pattern-non-formed region in which the pattern is not formed, the method comprising: a surface treatment step of contacting the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate with a surface treatment agent composition that is a liquid containing a silylating agent and a solvent; and on the surface of the pattern non-forming region after the surface treatment step, The contact angle of IPA with 2-propanol is 2° or more, and / or An evaluation step for determining whether the water contact angle with pure water is 50° or more. A processing method comprising:

27. A surface treatment agent composition used for treating a main surface of a semiconductor substrate, the main surface of the substrate having a pattern-formed region in which a pattern having a relief structure with a pattern dimension of 30 nm or less is formed, and a pattern-non-formed region in which the pattern is not formed, comprising: a liquid containing a silylating agent and a solvent, The IPA contact angle, determined by the following procedure, is 2° or more, and / or The water contact angle, determined by the following procedure, is 50° or more. Surface treatment composition. (procedure) The surface treatment agent composition is brought into contact with the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate. After contacting the surface treatment agent composition, on the surface of the pattern non-forming region, The contact angle with 2-propanol was measured at room temperature of 25°, and the measured value was taken as the IPA contact angle (°). The contact angle with pure water is measured at room temperature of 25°, and the measured value is taken as the water contact angle (°).

28. The surface treatment agent composition according to claim 27, The surface treatment agent composition, wherein the silylating agent has a trialkylsilyl group.

29. The surface treatment agent composition according to claim 27 or 28, The surface treatment agent composition, wherein the solvent comprises an aprotic solvent.

30. The surface treatment agent composition according to claim 29, The surface treatment agent composition, wherein the aprotic solvent comprises one or more solvents selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxides, carbonate solvents, polyhydric alcohol derivatives, nitrogen-containing solvents, and silicone solvents.

31. The surface treatment agent composition according to any one of claims 27 to 30, the silylating agent comprises one or more selected from the group consisting of hexamethyldisilazane, heptamethyldisilazane, N-(trimethylsilyl)dimethylamine, bis(dimethylamino)dimethylsilane, bis(trimethylsilyl)trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-trimethylsilylimidazole, trimethylsilyltriazole, bistrimethylsilyl sulfate, 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, hexamethyldisiloxane, trimethylsilyltrifluoroacetate, trimethylsilyltrifluoromethanesulfonate, trimethylsilylbenzenesulfonate, and trimethylsilyltoluenesulfonate; the solvent comprises one or more selected from the group consisting of propylene carbonate, a linear hydrocarbon solvent having 7 to 10 carbon atoms, menthane, pinane, γ-butyrolactone, propylene glycol monomethyl ether acetate, and 3-methoxy-3-methyl-1-butyl acetate.

32. The surface treatment agent composition according to any one of claims 27 to 31, The surface treatment agent composition comprises a catalyst.

33. The surface treatment agent composition according to claim 32, The catalyst is selected from the group consisting of trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, decyldimethylsilyl a surface treatment agent composition comprising one or more compounds selected from the group consisting of methyltrifluoromethanesulfonate, a sulfonic acid represented by the following general formula [3], an anhydride of the sulfonic acid, a salt of the sulfonic acid, a sulfonic acid derivative represented by the following general formula [4], a sulfonic acid ester represented by the following general formula [5], a sulfonimide represented by the following general formulas [6] and [7], a sulfonimide derivative represented by the following general formulas [8] and [9], a sulfonmethide represented by the following general formula [10], a sulfonmethide derivative represented by the following general formula [11], an acid imide, a nitrogen-containing compound, a nitrogen-containing heterocyclic compound, and a silylated heterocyclic compound. R ８ -S(=O) ２ OH [3] [In the above general formula [3], R ８ is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and hydroxyl groups. R ８’ -S (=O) ２ O-Si (H) ３－ｒ (R) ９ ) ｒ [4] [In the above general formula [4], R ８’ is a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R ９ are each independently at least one group selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and r is an integer of 1 to 3. R １０ -S(=O) ２ OR １１ [5] [In the above general formula [5], R １０ is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R １１ is a monovalent alkyl group having 1 to 18 carbon atoms. (R １２ -S(=O) ２ ) ２ NH [6] [In the above general formula [6], R １２ are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and elemental fluorine. 【Chemistry 3】 [In the above general formula [7], R １３ is a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms. (R １４ -S (=O) ２ ) ２ N) ｓ Si (H) ｔ (R) １５ ) ４－ｓ－ｔ [8] [In the above general formula [8], R １４ are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R １５ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, s is an integer of 1 to 3, t is an integer of 0 to 2, and the sum of s and t is 3 or less. 【Chemistry 4】 [In the above general formula [9], R １６ are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R １７ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, u is an integer of 1 to 3, v is an integer of 0 to 2, and the sum of u and v is 3 or less. (R １８ -S(=O) ２ ) ３ CH [10] [In the above general formula [10], R １８ are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and elemental fluorine. (R １９ -S (=O) ２ ) ３ C) ｗ Si (H) ｘ (R) ２０ ) ４－ｗ－ｘ [11] [In the above general formula [11], R １９ are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R ２０ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, w is an integer of 1 to 3, x is an integer of 0 to 2, and the sum of w and x is 3 or less.

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