Surface treatment method for semiconductor substrate and surface treatment composition

Abstract

This surface treatment method for semiconductor substrates treats a main surface of a semiconductor substrate which has, on the main surface, a pattern formation region where a pattern having a relief structure with a pattern size of 30 nm or less is formed, and a bevel region that is formed on the periphery of the pattern formation region; and this surface treatment method for semiconductor substrates comprises a surface treatment step wherein a surface treatment agent composition that contains a silylating agent is brought into contact with the pattern formation region and the bevel region on the main surface of the semiconductor substrate. With respect to the surface of the silicon oxide substrate, which has been surface treated by being brought into contact with the surface treatment agent composition, the IPA receding angle is 3° or more at the room temperature of 25°C and / or the water receding angle is 40° or more at the 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. Patent Document 1, for example, describes a surface treatment method for semiconductor substrates in which a water-repellent protective film is formed on the surface of the semiconductor substrate, thereby cleaning and drying the substrate while preventing pattern collapse (see paragraphs 0006, 0007, etc. of the patent document). Specifically, FIG. 8 of Patent Document 1 shows a graph illustrating the relationship between the cleaning sequence and the contact angle of water with respect to the pattern. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-114414 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 manufacturing stability. [Means for solving the problem]

[0005] As a result of further investigation, the present inventors have obtained the following findings. In a typical structure at the edge of a semiconductor substrate, in the upper bevel or front shoulder region from the top edge (approximately horizontal plane) to the edge face (approximately vertical plane), the angle with the top edge increases from 0 degrees to 90 degrees. That is, at the edge of the semiconductor substrate, there is an inclined surface that forms an angle of any value between 0 degrees and 90 degrees. In the manufacturing process of a semiconductor substrate, when a main surface having a pattern formation region on which a fine pattern is formed is rinsed with a rinse solution such as water or an organic solvent, it has been found that the rinse solution does not drain properly at the edge of the semiconductor substrate and may flow down the inclined surface to the back surface.

[0006] Based on this finding, the inventors further conducted extensive research and found that by performing surface treatment on a bevel region formed on the peripheral edge of a semiconductor substrate using a surface treatment agent composition that sets the receding angle of 2-propanol (hereinafter also referred to as "IPA") and / or the receding angle of pure water to a predetermined value, the liquid drainage characteristics of the rinse solution in the bevel region can be controlled; by using the IPA receding angle and / or the water receding angle as an index, the liquid drainage characteristics can be stably evaluated; and further, by setting the IPA receding angle and / or the water receding angle to a predetermined value or more, the rinse solution can be prevented from leaking onto the back surface of the semiconductor substrate during the manufacturing process, which led to the completion of the present invention.

[0007] According to the present invention, 1. A method for processing a main surface of a semiconductor substrate having a pattern formation region on a main surface of the substrate, the pattern having a relief structure with a pattern dimension of 30 nm or less, and a bevel region formed on a periphery of the pattern formation region, the method comprising: a surface treatment step of contacting the pattern formation region and the bevel region of the main surface of the semiconductor substrate with a surface treatment agent composition containing a silylating agent, It is required by the following steps: The IPA sweepback angle is 3° or greater at room temperature (25°C), and / or The water receding angle is 40° or more at room temperature of 25°. A processing method is provided. (procedure) The surface treatment agent composition is brought into contact with the surface of a silicon oxide substrate having a smooth surface and made of silicon oxide, thereby performing surface treatment. While the substrate was placed on a horizontal table, 3 μl of 2-propanol was dropped onto the surface of the surface-treated silicon oxide substrate at room temperature of 25°C, and the contact angle was measured 60 seconds later, and this value was designated as the IPA receding angle (°). While the substrate is placed on a horizontal table, 30 μl of pure water is dropped onto the surface of the surface-treated silicon oxide substrate at room temperature of 25°C, and the pure water is then sucked in at a rate of 6 μl / sec. The contact angle is measured while the droplet size is decreasing, and this value is defined as the water receding angle (°).

[0008] Further, according to the present invention, A surface treatment agent composition used for treating a main surface of a semiconductor substrate having a pattern formation region on a main surface of the substrate, the pattern having a relief structure with a pattern dimension of 30 nm or less, and a bevel region formed on a periphery of the pattern formation region, the composition comprising: a silylating agent, The IPA sweepback angle, as determined by the above procedure, is 3° or greater at room temperature (25°C), and / or The water receding angle obtained by the above procedure is 40° or more at room temperature of 25°. A surface treatment composition is provided. [Effects of the Invention]

[0009] According to the present invention, there are provided a method for treating the surface of a semiconductor substrate, which is excellent in production stability, and a surface treatment agent composition used therein. [Brief explanation of the drawings]

[0010] [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

[0011] 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.

[0012] 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 a pattern formation region on the main surface of the substrate, in which a pattern having a concave-convex structure with a pattern dimension of 30 nm or less is formed, and a bevel region formed on the periphery of the pattern formation region. This treatment method includes a surface treatment step of contacting a pattern formation region and a bevel region of a main surface of a semiconductor substrate with a surface treatment agent composition containing a silylating agent, and the method achieves an IPA receding angle of 3° or more at room temperature and 25° and / or a water receding angle of 40° or more at room temperature and 25°, as determined by the following procedure.

[0013] The above-mentioned Patent Document 1 does not disclose at all the formation of a water-repellent protective film on the bevel at the peripheral edge of the wafer. However, the present inventors have found that increasing the IPA sweep angle and / or water sweep angle by using a surface treatment agent composition used for the surface treatment of the bevel improves the ease of drainage of the rinse solution at the wafer edge.

[0014] According to the findings of the present inventors, it has been found that the liquid drainage characteristics of the rinse solution on the bevel region can be controlled by using the receding angle of 2-propanol (hereinafter referred to as the IPA receding angle) and / or the receding angle of pure water (hereinafter referred to as the water receding angle) as an index representing the characteristics of the surface treatment agent composition used on the bevel region formed on the peripheral edge of the semiconductor substrate. As a result of further investigation, it has been found that by setting the IPA receding angle and / or the water receding angle to be equal to or greater than the above-mentioned lower limit, it is possible to prevent the rinse solution from spreading to the back surface of the semiconductor substrate during the manufacturing process. In the case of the spin method, if the last liquid supplied before the drying process runs through to the back side, it is necessary to thoroughly dry the back side in addition to the main surface, which can lengthen the drying time. Therefore, it was found that it is preferable to minimize the amount of liquid running through to the back side before the drying process.

[0015] Although the detailed mechanism is not clear, it is thought that by appropriately increasing the IPA receding angle and / or the water receding angle, it is possible to appropriately control the ease with which the rinse liquid flows on the inclined surface that has been surface-treated with the surface treatment agent composition. Therefore, for example, when attempting to shake off a rinse liquid such as IPA or water using a spin, the rinse liquid flowing out from the top edge can be successfully shaken off by the front bevel or front shoulder before reaching the end face, and therefore the rinse liquid can be prevented from flowing around to the back surface via the end face.

[0016] In the processing method of this embodiment, when the front surface of the semiconductor substrate is rinsed with a rinse solution such as an aqueous solution or a non-aqueous solution such as IPA or an alcohol, after the surface treatment, the rinse solution is well drained off from the inclined surface, and therefore, in the case of spin cleaning, the rinse solution can be prevented from flowing around to the back surface of the semiconductor substrate, thereby improving manufacturing stability.

[0017] 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 inventors have found that in order to improve the ease of drainage of the IPA or water, it is desirable for the surface treatment agent layer formed by the surface treatment to have a larger IPA sweepback angle and / or a larger water sweepback angle.

[0018] Furthermore, in some embodiments, the rinse solution after surface treatment (the "second rinse solution" described below) may be water and IPA rinsed sequentially (e.g., "surface treatment → water rinse → IPA rinse" or "surface treatment → IPA rinse → water rinse"), and the inventors have found that in such embodiments, a large IPA sweep back angle and / or a large water sweep back angle is desirable.

[0019] The IPA sweepback angle is 3° or more, preferably 5° or more, more preferably 6° or more, and even more preferably 7° or more at room temperature of 25°; and / or The water receding angle at room temperature of 25° is 40° or more, preferably 50° or more, more preferably 60° or more, and even more preferably 70° or more. This can prevent the rinse solution from getting around to the back surface of the semiconductor substrate. On the other hand, the IPA sweepback angle may be set to, for example, 20° or less, and the water sweepback angle may be set to, for example, 100° or less.

[0020] Furthermore, the standard deviation of the IPA sweepback angle at 10 predetermined points on the surface can be set to, for example, 5° or less, and the difference between the maximum and minimum values of the IPA sweepback angle can be set to, for example, 10° or less. Similarly, the standard deviation of the water sweep-back angles at 10 predetermined points on the surface can be set to, for example, 5° or less, and the difference between the maximum and minimum values of the water sweep-back angles can be set to, for example, 10° or less.

[0021] 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 formation region on a main surface of the substrate, the pattern having a relief structure with a pattern dimension of 30 nm or less, and a bevel region formed on a periphery of the pattern formation region, the method comprising: a surface treatment step of contacting the pattern formation region and the bevel region of the main surface of the semiconductor substrate with a surface treatment agent composition containing a silylating agent; and On the main surface of the semiconductor substrate after the surface treatment step, IPA sweepback angle is 3° or more, and / or An evaluation step for determining whether the water receding angle is 40° or more. Includes: In the evaluation step of the above embodiment, the IPA receding angle and / or the water receding angle may be measured and evaluated in a region of the main surface where no pattern is formed (non-pattern region). In addition, the evaluation process of the above embodiment may be performed by making a judgment using the results of measuring the IPA receding angle and / or the water receding angle for a substrate (dummy substrate) having a smooth surface made of the same material as the main surface of the semiconductor substrate. According to the above-described embodiment, by including a step of evaluating the IPA receding angle and / or the water receding angle in the processing method (measurement in a non-patterned region after each substrate processing or after each fixed number of substrate processing, or measurement on a dummy substrate after each fixed number of substrate processing), it is possible to confirm for each substrate whether the surface treatment step in which the surface treatment agent composition is brought into contact has been properly performed. Therefore, when an abnormality occurs in a specific substrate among the substrates processed by the processing method of this embodiment, such as the amount of backside transfer being unable to be suppressed, it becomes easy to determine the cause: whether the above-described surface treatment step was not properly performed or whether the subsequent step of shaking off the rinse liquid, etc., was not properly performed.

[0022] Furthermore, the contact angle of 2-propanol on the substrate surface treated with the surface treatment agent composition is preferably 2° or more and 10° or less, more preferably 3° or more and 10° or less, at room temperature (25°), thereby making it possible to reduce the rate of pattern collapse in the pattern formation region. Similarly, the lower limit of the water contact angle on the substrate surface treated with the surface treatment agent composition is, for example, preferably 50° or more, more preferably 60° or more, at room temperature of 25°C. This makes it possible to reduce the rate of pattern collapse in the pattern formation region. On the other hand, the upper limit of the water contact angle is not particularly limited, but may be, for example, 110° or less at room temperature of 25°C.

[0023] According to this embodiment, a surface treatment agent layer can be formed on the main surface of the substrate by contacting the main surface with the surface treatment agent composition in the surface treatment step. As a result, the surface treatment agent layer on the pattern formation region can suppress pattern collapse, and the surface treatment agent layer on the bevel region can suppress transfer to the back surface.

[0024] Furthermore, 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 sweepback angle and / or water sweepback angle even on 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.

[0025] The surface treatment agent composition of the present embodiment is used to treat a main surface of a semiconductor substrate having a pattern formation region on the main surface of the substrate, where a pattern having an uneven structure with a pattern dimension of 30 nm or less is formed, and a bevel region formed on the periphery of the pattern formation region. Such a surface treatment agent composition contains a silylating agent and is configured so that the IPA receding angle, determined by the following procedure, is 3° or more at room temperature at 25°C, and / or the water receding angle, determined by the following procedure, is 40° or more at room temperature at 25°C.

[0026] The IPA sweepback angle on the substrate surface treated with the surface treatment agent composition can be determined by the following procedure. The surface of a silicon oxide substrate having a smooth surface and made of silicon oxide is brought into contact with a surface treatment composition to perform surface treatment. While the substrate is placed on a horizontal table, 3 μl of 2-propanol is dropped onto the surface of the surface-treated silicon oxide substrate at room temperature of 25°C, and the contact angle is measured 60 seconds later, and this value is defined as the IPA receding angle (°). 60 seconds after the droplet was dropped, the 2-propanol had dried and the contact area between the droplet and the substrate had decreased, so the contact angle at this time could be considered to be the IPA receding angle. The water receding angle on the surface of a substrate treated with the surface treatment agent composition can be determined by the following procedure. The surface treatment is performed by bringing the surface treatment composition into contact with the main surface of a silicon oxide substrate having a smooth surface and made of silicon oxide. A 30 μl drop of pure water was dropped onto the surface of a surface-treated silicon oxide substrate placed on a horizontal table at room temperature of 25°C, and the pure water was then sucked up at a rate of 6 μl / sec to reduce the droplet size. The contact angle of the droplet was continuously measured during this process, and the contact angle at which the droplet size decreased without changing the contact angle was determined, and this value was taken as the water receding angle (°).

[0027] The surface of the silicon oxide substrate is preferably an oxide film, but may contain small amounts of other components such as unavoidable silicon.

[0028] During the process of forming a film that constitutes a semiconductor element in a pattern formation region, silicon or silicon nitride films may be present in the bevel region or edge, resulting in an exposed film containing a mixture of different materials. Even in such cases, by using a surface treatment agent composition that imparts the above-mentioned IPA and / or water receding angle, it is possible to stably suppress the rinsing solution from seeping onto the back surface of the semiconductor substrate.

[0029] A separate, smooth substrate made of the same material as the main surface of the semiconductor substrate may be used as the measurement substrate for measuring the IPA and water sweep angles. Furthermore, in the case of a semiconductor substrate having a smooth surface with no pattern formed thereon, the same substrate as the semiconductor substrate may be used, i.e., measurements may be performed in the patterned area of the semiconductor substrate.

[0030] The IPA contact angle or water contact angle of the main surface that has been surface-treated with the surface treatment agent composition can be determined by the following procedure. The surface of a silicon oxide substrate (substrate for evaluation) having a smooth surface and made of silicon oxide is brought into contact with the surface treatment composition to perform surface treatment. While the surface-treated silicon oxide substrate is placed on a horizontal table, 1 μl of 2-propanol or pure water is dropped onto the surface at room temperature of 25°C, and the static contact angle is measured 5 seconds later, and this value is taken as the IPA contact angle (°) or water contact angle (°). The substrate for evaluating the IPA contact angle or water contact angle may be one that meets the same conditions as the IPA receding angle or water receding angle. The above-mentioned procedures for measuring the receding angle and contact angle are 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 measurement procedure for the receding angle and contact angle may be adopted, applying one of the following measurement conditions: a measurement temperature of 23°±5°C for the receding angle and contact angle, a droplet volume of 0.1 μl to 5 μl, and a measurement timing of 0.1 seconds to 30 seconds after dropping.

[0031] In this embodiment, the IPA receding angle, water receding angle, IPA contact angle, and 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 the composition promptly after preparation, etc. can be cited as factors for setting the IPA receding angle, water receding angle, IPA contact angle, and water contact angle within the desired numerical range. In this specification, immediately after or immediately before means within 24 hours, preferably within 2 hours, and particularly preferably within 30 minutes.

[0032] 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.

[0033] (Method of manufacturing semiconductor substrate) The method for manufacturing a semiconductor substrate according to this embodiment will now be described in detail.

[0034] 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.

[0035] 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.

[0036] First, a substrate 10 having a pattern (relief structure 20) formed on a main surface 12 is prepared.

[0037] 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.

[0038] 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.

[0039] 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, and oxides, nitrides, nitrogen oxides, carbonitrides, and carbonoxides containing one or more 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.

[0040] 1 has, on a 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. Of course, the processing target may also be a substrate that does not have a pattern-non-forming region.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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 .

[0048] 1 and 2, substrate 10 has a bevel region 50 formed on at least a portion of the edge of substrate 10. Bevel region 50 may have an inclined surface (bevel) formed on 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.

[0049] 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, etc. These may be used alone or in combination of two or more.

[0050] 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.

[0051] 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).

[0052] 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.

[0053] 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.

[0054] 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.

[0055] The method of supplying the surface treatment agent composition 60 includes a single wafer method, typified by a spin method (spin coating method), in which the wafers are held one by one almost horizontally and rotated while the composition is supplied near the center of rotation, replacing cleaning liquid and the like retained in the uneven pattern of the wafer, and filling the wafer with the composition.

[0056] 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 .

[0057] The surface treatment agent layer 70 is formed on the main surface 12 of the substrate 10 in the pattern formation region 30 and the bevel region 50, and if the substrate 10 has a pattern non-formation region 32, the surface treatment agent layer 70 may also be formed in the pattern non-formation region 32. The surface treatment agent layer 70 may also be formed on the end surface 54 or the lower bevel 55.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] In this manner, a semiconductor substrate (substrate 10) using the surface treatment agent composition of this embodiment is obtained.

[0065] 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.

[0066] 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.

[0067] Next, the surface treatment agent composition used for the surface treatment of the semiconductor substrate will be described.

[0068] 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.

[0069] R 1 a Si(H) b X4-a-b [1]

[0070] 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.

[0071] 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.

[0072] 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 6are 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 (where, 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.

[0073] 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, C8H17 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 18 H 37 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 11 Si(CH3)(NH2)2、C6H 13 Si(CH3)(NH2)2、C7H 15 Si(CH3)(NH2)2、C8H 17 Si(CH3)(NH2)2、C9H 19 Si(CH3)(NH2)2、C 10 H 21 Si(CH3)(NH2)2、C 11 H 23 Si(CH3)(NH2)2、C 12 H 25 Si(CH3)(NH2)2、C 13 H 27 Si(CH3)(NH2)2、C 14 H 29 Si(CH3)(NH2)2、C 15 H 31 Si(CH3)(NH2)2、C 16 H 33 Si(CH3)(NH2)2、C 17 H 35 Si(CH3)(NH2)2、C 18 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"> 17CH2CH2Si(NH2)3, CF3CH2CH2Si(CH3)(NH2)2, C2F5CH2CH2Si(CH3)(NH2)2, C3F7CH2CH2Si(CH3)(NH2)2, C4F9CH2CH2Si(CH3)(NH2)2, C5F 11 CH2CH2Si(CH3)(NH2)2, CF 13 CH2CH2Si(CH3)(NH2)2, C7F 15 CH2CH2Si(CH3)(NH2)2, C8F 17 CH2CH2Si(CH3)(NH2)2, CF3CH2CH2Si(CH3)2NH2, C2F5CH2CH2Si(CH3)2NH2, C3F7CH2CH2Si(CH3)2NH2, C4F9CH2CH2Si(CH3)2NH2, C5F 11 CH2CH2Si(CH3)2NH2, CF 13 CH2CH2Si(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 4are each independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms. 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 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. For example, 2-trimethylsilyl-1,1,3,3-tetramethylguanidine, -N(R 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 a6each independently represents a hydrogen atom or an organic group, R a4 , R a5 and R a6 is at least 1. For example, -N(R) is a methyl group, and -N(R) is a methyl group. a7 )-C(=O)R a8 (where, 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.

[0074] 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 (Here, 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.).

[0075] 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.

[0076] 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.

[0077] 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.).

[0078] 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.

[0079] 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 water-repellent properties 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] R 2 c (H) d Si-X [2]

[0084] 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.

[0085] 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.

[0086] 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 elemental fluorine. [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 elemental fluorine. ((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.

[0087] 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.

[0088] 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.

[0089] 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.]

[0090] 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.

[0091] 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.

[0092] 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.

[0093] The surface treatment agent composition may contain a solvent.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] Examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, cyclohexanone, and isophorone.

[0100] 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.

[0101] Examples of the sulfoxide solvent include dimethyl sulfoxide.

[0102] Examples of the carbonate solvent include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] Examples of the silicone solvent include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane.

[0107] 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.

[0108] 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.

[0109] 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. 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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 formation region on the main surface of the substrate, in which a pattern having a concave-convex structure with a pattern dimension of 30 nm or less is formed, and a bevel region formed on the periphery of the pattern formation region, comprising: a surface treatment step of contacting the pattern formation region and the bevel region of the main surface of the semiconductor substrate with a surface treatment agent composition containing a silylating agent, The IPA sweepback angle, as determined by the following procedure, is 3° or greater at room temperature of 25°C, and / or The water receding angle, calculated using the following procedure, is 40° or more at room temperature of 25°C. Processing method. (procedure) The surface treatment agent composition is brought into contact with the surface of a silicon oxide substrate having a smooth surface and made of silicon oxide, thereby performing surface treatment. The surface of the surface-treated silicon oxide substrate is placed on a horizontal table. At room temperature of 25°C, 3 μl of 2-propanol was dropped, and the contact angle was measured 60 seconds later, and this value was taken as the IPA receding angle (°). At room temperature of 25°C, 30 μl of pure water is dropped, and then the pure water is sucked up at a rate of 6 μl / sec. The contact angle is measured while the droplet size is decreasing, and this value is defined as the water receding angle (°). 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 of the semiconductor substrate and / or at least one height dimension in a direction perpendicular to the main surface of the semiconductor substrate. 3. The treatment method according to 1. or 2., 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. 4. The processing method according to any one of 1. to 3., The treatment method, wherein the surface treatment agent composition contains a solvent. 5. The processing method according to 4., The method of processing wherein the solvent comprises an aprotic solvent. 6. The processing method according to 5., A processing method in which the solvent contains the aprotic solvent in an amount of 100 mass % relative to 100 mass % of the solvent. 7. The processing method according to 5. or 6., 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. 8. The processing method according to any one of 5. to 7., The process wherein the solvent comprises a carbonate solvent or a lactone. 9. The processing method according to any one of 5. to 7., The process, wherein the solvent comprises propylene carbonate or gamma-butyrolactone. 10. The processing method according to any one of 5. to 7., The method of processing, wherein the solvent comprises a derivative of a polyhydric alcohol. 11. The processing method according to any one of 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 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. 12. The processing method according to any one of 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 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 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 1. to 14., The treatment method, wherein the surface treatment agent composition contains a catalyst. 16. The method according to 15, 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 12are 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.] TIFF0007727203000007.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. TIFF0007727203000008.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. 17. The method according to 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 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 processing method according to any one of 1. to 18., The IPA sweepback angle is 5° or more at room temperature of 25°C, and / or The water receding angle is 50° or more at room temperature of 25°. Processing method. 20. The processing method according to any one of 1. to 19., The IPA contact angle, measured by the following procedure, is 2° or more and 10° or less at room temperature (25°C), and / or The water contact angle measured by the following procedure is 50° or more at room temperature (25°C). Processing method. (procedure) The surface treatment agent composition is brought into contact with the surface of a silicon oxide substrate having a smooth surface and made of silicon oxide, thereby performing surface treatment. The surface of the surface-treated silicon oxide substrate is placed on a horizontal table. At room temperature of 25°C, 1 μl of 2-propanol was dropped onto the sample, and the contact angle was measured 5 seconds later. This value was designated as the IPA contact angle (°). At room temperature of 25°C, 1 μl of pure water is dropped, and the contact angle is measured 5 seconds later, and this value is taken as the water contact angle (°). 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 formation region on the main surface of the substrate, in which a pattern having a concave-convex structure with a pattern dimension of 30 nm or less is formed, and a bevel region formed on the periphery of the pattern formation region, comprising: a surface treatment step of contacting the pattern formation region and the bevel region of the main surface of the semiconductor substrate with a surface treatment agent composition containing a silylating agent; and On the main surface of the semiconductor substrate after the surface treatment step, IPA sweepback angle is 3° or more, and / or An evaluation step for determining whether the water receding angle is 40° or more. A processing method comprising: 28. A surface treatment composition used to treat the main surface of a semiconductor substrate having a pattern formation region on the main surface of the substrate, on which a pattern having a relief structure with a pattern dimension of 30 nm or less is formed, and a bevel region formed on the periphery of the pattern formation region, comprising: a silylating agent, The IPA sweepback angle, as determined by the following procedure, is 3° or greater at room temperature of 25°C, and / or The water receding angle, calculated using the following procedure, is 40° or more at room temperature of 25°C. Surface treatment composition. (procedure) The surface treatment agent composition is brought into contact with the surface of a silicon oxide substrate having a smooth surface and made of silicon oxide, thereby performing surface treatment. The surface of the surface-treated silicon oxide substrate is placed on a horizontal table. At room temperature of 25°C, 3 μl of 2-propanol was dropped, and the contact angle was measured 60 seconds later, and this value was taken as the IPA receding angle (°). At room temperature of 25°C, 30 μl of pure water is dropped, and then the pure water is sucked up at a rate of 6 μl / sec. The contact angle is measured while the droplet size is decreasing, and this value is defined as the water receding 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.] TIFF0007727203000009.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. TIFF0007727203000010.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]

[0115] 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.

[0116] <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."

[0117] (Surface treatment composition 2) 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. Trifluoroacetic acid (TFA) was then added and reacted with TMSDMA to prepare surface treatment composition 2 containing 0.1 mass% trimethylsilyl trifluoroacetate (TMSTFA) as compound A and 1 mass% TMSDMA as a silylating agent. Surface treatment composition 2 was used immediately after preparation for the surface treatment described below.

[0118] (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.

[0119] (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. For the surface treatment described below, surface treatment agent compositions 4 to 37 were used immediately after preparation. The abbreviations in Table 1 and the names of the compounds are listed in Table 2.

[0120] <Preparing the backside evaluation board> A silicon oxide wafer was prepared, which had a main surface with a smooth thermal oxide film and a bevel region on the periphery where an inclined surface (upper bevel) was formed, and an end face at the end of the main surface that was at an angle of 90 degrees to the main surface. The prepared silicon oxide wafer was immersed in a 1% by mass aqueous solution of hydrofluoric acid at room temperature for 10 minutes, then in pure water at room temperature for 1 minute, and then in 2-propanol (IPA) at room temperature for 1 minute, and finally dried to prepare a substrate for backside evaluation.

[0121] <Manufacturing of patterned substrates> 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. The surface of the prepared substrate was dry cleaned by UV / O3 irradiation. As a result, the surface of the substrate was oxidized to silicon oxide. In this way, a substrate with a pattern formed was prepared. Hereinafter, the portion having the convex structure will be referred to as a "pattern formation region." The main surface of the backside evaluation substrate and the main surface of the substrate on which the pattern is formed are made of the same material (silicon oxide).

[0122] [Table 1]

[0123] [Table 2]

[0124] <Substrate surface treatment> [Examples I-1 to I-37, Comparative Example I-1] The above substrate was placed on a spin coater, and while rotating the substrate at a speed of 200 rpm, it was discharged at a speed of 200 cc / min in the order of IPA, the surface treatment agent composition described in Table 1, and IPA. After the discharge stopped, an attempt was made to continue rotating to shake off the IPA. In Comparative Example I-1, the surface treatment agent composition was not discharged, and the same treatment as in Examples I-1 to I-37 was performed otherwise.

[0125] [Examples W-1 to W-37, Comparative Example 2] The above substrate was placed on a spin coater, and while rotating the substrate at a speed of 200 rpm, it was discharged at a speed of 200 cc / min in the order of IPA, the surface treatment agent composition described in Table 1, and water. After the discharge stopped, an attempt was made to continue rotating to shake off the water. In Comparative Example W-1, the surface treatment agent composition was not discharged, and the same treatment as in Examples W-1 to W-37 was performed otherwise.

[0126] <Evaluation of reverse side of IPA, reverse side of water, IPA receding angle, water receding angle, IPA contact angle, water contact angle> The substrate for reverse side evaluation obtained by the above "surface treatment of the substrate" was taken out from the spin coater, and the distance of the reverse side from the end face of the substrate was measured. The measurement was performed at 8 locations at equal intervals and the average value was calculated. The average value of the reverse side distance is shown in Tables 3 and 4. Furthermore, after drying the above substrate, at room temperature of 25 degrees, it was set on a contact angle meter and placed on a horizontal stage. Approximately 3 μL of IPA was dropped, and the contact angle (contact angle (°) 60 seconds after dropping IPA) when the IPA droplet had naturally dried and the droplet size had become smaller was measured as the IPA receding angle. The IPA receding angle is shown in Tables 3 and 4. Also, after drying the above substrate, at room temperature of 25 degrees, it was set on a contact angle meter and placed on a horizontal stage. 30 μl of pure water was dropped, and then the pure water was aspirated at a speed of 6 μl / second to reduce the droplet size. The contact angle of the droplet during this process was continuously measured, and the contact angle when the droplet size became smaller without the contact angle changing was measured as the water receding angle. The water receding angle is shown in Tables 3 and 4.

[0127] The substrate used to measure the IPA receding angle was then set in a contact angle meter after drying, and placed on a horizontal table. Approximately 1 μL of IPA was dropped onto the substrate, and the state of the droplet was observed after 5 seconds. The contact angle (°) at this time was measured as the IPA contact angle. The IPA contact angles are shown in Tables 3 and 4. The substrate used to measure the water receding angle was then set in a contact angle meter after drying, and placed on a horizontal table. Approximately 1 μL of pure water was dropped onto the substrate, and the state of the droplet was observed after 5 seconds. The contact angle (°) at this time was measured as the water contact angle. The water contact angles are shown in Tables 3 and 4.

[0128] <Evaluation of pattern collapse rate> In the "substrate surface treatment" for the substrate on which the above pattern was formed, after the final IPA discharge, the substrate was dried while N2 was discharged onto the substrate. The pattern formation area of ​​the substrate was observed with 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 that had collapsed was counted. The ratio of convex portions that had collapsed to all convex portions is shown in Tables 3 and 4 as the pattern collapse rate (%).

[0129] [Table 3]

[0130] [Table 4]

[0131] As shown in Tables 3 and 4, Examples I-1 to I-37 and Examples W-1 to W-37, which used surface treatment agent compositions 1 to 37, exhibited IPA receding angles and water receding angles equal to or greater than the predetermined values. Furthermore, as shown in Tables 3 and 4, the backwashing of the rinse solution was reduced compared to Comparative Examples I-1 and W-1, which were not treated with the surface treatment agent composition.

[0132] Furthermore, as shown in Tables 3 and 4, Examples I-1 to I-37 and Examples W-1 to W-37, which used surface treatment agent compositions 1 to 37, were able to exhibit IPA contact angles and water contact angles equal to or greater than the predetermined values, and as shown in Tables 3 and 4, showed a better pattern collapse suppression effect than Comparative Example I-1 and Comparative Example W-1.

[0133] This application claims priority based on Japanese Patent Application No. 2020-089228, filed on May 21, 2020, and Japanese Patent Application No. 2020-089232, filed on May 21, 2020, the disclosures of which are incorporated herein in their entireties. [Explanation of symbols]

[0134] 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. A processing method for processing a main surface of a semiconductor substrate having a pattern formation region on a main surface of the substrate, the pattern having a relief structure with a pattern dimension of 30 nm or less, and a bevel region formed on a periphery of the pattern formation region and having an inclined surface, the method comprising: a surface treatment step of contacting the pattern formation region and the bevel region of the main surface of the semiconductor substrate with a liquid surface treatment agent composition containing a silylating agent and a solvent by a spin method; after the surface treatment step, bringing the main surface of the semiconductor substrate into contact with a rinse solution and spinning off the rinse solution; Including, The IPA sweepback angle, determined by the following procedure, is 3° or more at room temperature of 25°, and / or The water receding angle, determined by the following procedure, is 40° or more at room temperature of 25°. Processing method. (procedure) The surface treatment agent composition is brought into contact with the surface of a silicon oxide substrate having a smooth surface and made of silicon oxide, thereby performing surface treatment. The surface of the surface-treated silicon oxide substrate is placed on a horizontal table. At room temperature of 25°C, 3 μl of 2-propanol was dropped, and the contact angle was measured 60 seconds later, and this value was defined as the IPA receding angle (°). At room temperature of 25°C, 30 μl of pure water is dropped, and then the pure water is sucked up at a rate of 6 μl / sec. The contact angle is measured while the droplet size is decreasing, and this value is defined as the water receding angle (°).

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 of the semiconductor substrate and / or at least one height dimension in a direction perpendicular to the main surface of the semiconductor substrate.

3. 3. The processing method according to claim 1 or 2, 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.

4. The processing method according to any one of claims 1 to 3, The method of processing, wherein the solvent comprises an aprotic solvent.

5. 5. The processing method according to claim 4, The processing method, wherein the solvent contains the aprotic solvent in an amount of 100 mass % relative to 100 mass % of the solvent.

6. 6. The processing method according to claim 4 or 5, 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.

7. The processing method according to any one of claims 4 to 6, The process wherein the solvent comprises a carbonate solvent or a lactone.

8. The processing method according to any one of claims 4 to 6, The processing method, wherein the solvent comprises propylene carbonate or gamma-butyrolactone.

9. The processing method according to any one of claims 4 to 6, The method of processing, wherein the solvent comprises a derivative of a polyhydric alcohol.

10. The processing method according to any one of claims 1 to 9, 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.

11. The processing method according to any one of claims 1 to 10, The method of the present invention, wherein the silylating agent has a trialkylsilyl group.

12. The processing method according to any one of claims 1 to 11, The treatment method, wherein the element that bonds to the Si element in the silylating agent is nitrogen.

13. The processing method according to any one of claims 1 to 12, 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.

14. The processing method according to any one of claims 1 to 13, The treatment method, wherein the surface treatment agent composition contains a catalyst.

15. 15. The processing method of claim 14, 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 fluorine atoms. 【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 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.

16. 16. The processing method according to claim 14 or 15, 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.

17. The method according to any one of claims 1 to 16, 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.

18. The processing method according to any one of claims 1 to 17, The IPA sweepback angle is 5° or more at room temperature of 25°, and / or The water receding angle is 50° or more at room temperature of 25°. Processing method.

19. The method according to any one of claims 1 to 18, The IPA contact angle, measured by the following procedure, is 2° or more and 10° or less at room temperature of 25°, and / or The water contact angle measured by the following procedure is 50° or more at room temperature of 25°. Processing method. (procedure) The surface treatment agent composition is brought into contact with the surface of a silicon oxide substrate having a smooth surface and made of silicon oxide, thereby performing surface treatment. The surface of the surface-treated silicon oxide substrate is placed on a horizontal table. At room temperature of 25°C, 1 μl of 2-propanol was dropped onto the sample, and the contact angle was measured 5 seconds later. This value was designated as the IPA contact angle (°). At room temperature of 25° C., 1 μl of pure water is dropped, and the contact angle is measured 5 seconds later, and this value is taken as the water contact angle (°).

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 drying step of drying the main surface of the semiconductor substrate.

24. The processing method according to any one of claims 1 to 23, 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.

25. 1. A method for processing a main surface of a semiconductor substrate having a pattern formation region on a main surface of the substrate, the pattern having a concave-convex structure with a pattern dimension of 30 nm or less, and a bevel region formed on a periphery of the pattern formation region and having an inclined surface, the method comprising: a surface treatment step of contacting the pattern formation region and the bevel region of the main surface of the semiconductor substrate with a liquid surface treatment agent composition containing a silylating agent and a solvent by a spin method; and On the main surface of the semiconductor substrate after the surface treatment step, IPA sweepback angle is 3° or more, and / or an evaluation step of determining whether the water receding angle is 40° or more; a step of spinning off the rinse solution after the evaluation step; A processing method comprising:

26. A surface treatment agent composition for use in a treatment method in which a main surface of a semiconductor substrate having a pattern formation region on a main surface of the substrate, in which a pattern having a concave-convex structure with a pattern dimension of 30 nm or less is formed, and a bevel region formed on the periphery of the pattern formation region and having an inclined surface, is surface-treated with the surface treatment agent composition by a spin method, and then a rinse solution is shaken off by a spin method, the method comprising: a liquid containing a silylating agent and a solvent, The IPA sweepback angle, determined by the following procedure, is 3° or more at room temperature of 25°, and / or The water receding angle, determined by the following procedure, is 40° or more at room temperature of 25°. Surface treatment composition. (procedure) The surface treatment agent composition is brought into contact with the surface of a silicon oxide substrate having a smooth surface and made of silicon oxide, thereby performing surface treatment. The surface of the surface-treated silicon oxide substrate is placed on a horizontal table. At room temperature of 25°C, 3 μl of 2-propanol was dropped, and the contact angle was measured 60 seconds later, and this value was defined as the IPA receding angle (°). At room temperature of 25°C, 30 μl of pure water is dropped, and then the pure water is sucked up at a rate of 6 μl / sec. The contact angle is measured while the droplet size is decreasing, and this value is defined as the water receding angle (°).

27. The surface treatment agent composition according to claim 26, The surface treatment agent composition, wherein the silylating agent has a trialkylsilyl group.

28. The surface treatment agent composition according to claim 26 or 27, The surface treatment agent composition, wherein the solvent comprises an aprotic solvent.

29. The surface treatment agent composition according to claim 28, 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.

30. The surface treatment agent composition according to any one of claims 26 to 29, 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.

31. The surface treatment agent composition according to any one of claims 26 to 30, The surface treatment agent composition comprises a catalyst.

32. The surface treatment agent composition according to claim 31, 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. 【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 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.

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