Surface treatment method for semiconductor substrate and surface treatment agent composition

Abstract

The surface treatment method of the semiconductor substrate of the present invention is a treatment method for treating a main surface of a semiconductor substrate having a pattern formation region in which a pattern is formed on the main surface of the substrate and a bevel region formed on the periphery of the pattern formation region, the pattern having a concavo-convex structure with a pattern size of 30 nm or less, the method comprising a surface treatment step of bringing a surface treatment agent composition containing a silylating agent into contact with the pattern formation region and the bevel region of the main surface of the semiconductor substrate, the surface of the silicon dioxide substrate treated by bringing the surface treatment agent composition into contact having an IPA receding angle of 3° or more at room temperature of 25 degrees and / or a water receding angle of 40° or more at room temperature of 25 degrees.

Description

Technical Field

[0001] The invention relates to a surface treatment method for semiconductor substrates and a surface treatment agent composition. Background Technology

[0002] Various surface treatment methods for semiconductor substrates have been developed to date. Among such techniques, the one described in Patent Document 1 is known, for example. Patent Document 1 describes a surface treatment method for a semiconductor substrate that prevents pattern collapse by forming a water-repellent protective film on the surface of the semiconductor substrate and then cleaning and drying the substrate (paragraphs 0006, 0007, etc. in the Patent Document). Specifically, Figure 8 of Patent Document 1 shows a diagram illustrating the relationship between the cleaning sequence and the contact angle of water with the pattern.

[0003] Existing patent literature

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2010-114414 Summary of the Invention

[0006] The problem the invention aims to solve

[0007] However, the results of the inventors' research have clarified that there is room for improvement in the surface treatment method for semiconductor substrates described in the aforementioned Patent Document 1 in terms of manufacturing stability.

[0008] Solution for solving the problem

[0009] Further research by the inventors revealed the following insights.

[0010] In a typical structure at the end of a semiconductor substrate, the angle between the top edge and the front shoulder increases from 0 degrees to 90 degrees in the region of the upper slope and front shoulder from the top edge (which is generally horizontal) to the edge surface (which is generally vertical). That is, at the end of the semiconductor substrate, there is an inclined surface with an arbitrary angle greater than 0 degrees and less than 90 degrees.

[0011] It is known that during the manufacturing process of semiconductor substrates, when the main surface of the pattern forming area with fine patterns is rinsed with water, organic solvents or other rinsing solutions, there is a concern that the rinsing solution may not be properly removed from the ends of the semiconductor substrate and may instead flow along its inclined surface to the back side.

[0012] Further research based on this insight revealed that by performing surface treatment on 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 specified value on a beveled region formed at the periphery of a semiconductor substrate, the dehydration characteristics of the rinsing solution in the beveled region can be controlled. Not only can the dehydration characteristics be stably evaluated by using the IPA receding angle and / or the water receding angle as indicators, but by setting the IPA receding angle and / or the water receding angle to a value above the specified value, it is also possible to suppress the rinsing solution from flowing around to the back side of the semiconductor substrate during the manufacturing process, thus completing the present invention.

[0013] According to the present invention, a processing method is provided.

[0014] This is a processing method for processing the main surface of a semiconductor substrate having a patterned area and a beveled area formed around the periphery of the patterned area, wherein the pattern has a textured structure with a pattern size of 30 nm or less, and the method includes the following steps:

[0015] The surface treatment process involves contacting the surface treatment agent composition containing a silylating agent with the aforementioned patterned area and the aforementioned beveled area on the main surface of the aforementioned semiconductor substrate.

[0016] The IPA backlash angle determined by the following steps is 3° or more at room temperature (25°C), and / or

[0017] The water receding angle is above 40° at room temperature of 25 degrees Celsius.

[0018] (step)

[0019] The aforementioned surface treatment agent composition is brought into contact with the surface of a smooth silicon dioxide substrate to perform surface treatment.

[0020] With the substrate placed on a horizontal platform, for the surface of the aforementioned surface-treated silica substrate: 3 μL of 2-propanol was added dropwise at room temperature (25°C), and the contact angle was measured after 60 seconds. This value was taken as the aforementioned IPA receding angle (°).

[0021] With the surface of the aforementioned surface-treated silica substrate placed on a water platform, 30 μL of pure water was added dropwise at room temperature (25°C). Then, pure water was aspirated at a rate of 6 μL / second, and the contact angle during the droplet size reduction process was measured. This value was taken as the aforementioned water receding angle (°).

[0022] In addition, according to the present invention, a surface treatment agent composition is provided.

[0023] It is used to process the main surface of a semiconductor substrate having a patterned area and a beveled area formed around the patterned area, wherein the pattern has a textured structure with a pattern size of 30 nm or less.

[0024] The aforementioned surface treatment agent composition contains a silylating agent.

[0025] The IPA backlash angle calculated using the above steps is 3° or more at room temperature (25 degrees Celsius), and / or

[0026] The water receding angle calculated using the above steps is greater than 40° at a room temperature of 25 degrees Celsius.

[0027] The effects of the invention

[0028] According to the present invention, a surface treatment method for manufacturing a semiconductor substrate with excellent stability and a surface treatment agent composition for use therein are provided. Attached Figure Description

[0029] Figure 1 This is a top view schematic diagram showing the structure of a semiconductor substrate.

[0030] Figure 2 This is a cross-sectional schematic diagram showing the structure of a semiconductor substrate.

[0031] Figure 3 This is a schematic cross-sectional view showing the manufacturing process of a semiconductor substrate. Detailed Implementation

[0032] The embodiments of the present invention are described below using the accompanying drawings. It should be noted that in all the drawings, the same reference numerals are used for the same constituent elements, and descriptions are appropriately omitted. Furthermore, the figures are schematic diagrams and do not correspond to actual dimensions.

[0033] The surface treatment method for the semiconductor substrate of this embodiment is a method for treating the main surface of a semiconductor substrate having a pattern forming region and a beveled region formed around the pattern forming region, wherein the pattern has a concave-convex structure with a pattern size of 30 nm or less.

[0034] The processing method includes a surface treatment step in which a surface treatment agent composition containing a silylating agent is brought into contact with the patterned area and the beveled area of ​​the main surface of the semiconductor substrate, wherein the IPA back angle is 3° or more at room temperature of 25 degrees Celsius and / or the water back angle is 40° or more at room temperature of 25 degrees Celsius, as determined by the following steps.

[0035] Patent Document 1 does not disclose the formation of a water-repellent protective film on the beveled surface of the wafer periphery. On the other hand, the inventors have discovered that by using a surface treatment agent composition for surface treatment of the bevel to increase the IPA back angle and / or water back angle, the ease of removing the rinsing solution at the wafer end is improved.

[0036] According to the present inventors, it has been clarified that by using the retreat angle of 2-propanol (hereinafter referred to as the IPA retreat angle) and / or the retreat angle of pure water (hereinafter referred to as the water retreat angle) as indicators of the characteristics of the surface treatment agent composition used on the beveled region formed on the periphery of the semiconductor substrate, the descaling characteristics of the rinsing solution in the beveled region can be controlled. Further research has shown that by setting this IPA retreat angle and / or water retreat angle to or above the aforementioned lower limit value, it is possible to suppress the rinsing solution from wrapping around to the back side of the semiconductor substrate during the manufacturing process.

[0037] As the inventors have observed, in the case of a rotational process, if the last liquid supplied before the drying process flows around to the back side, then in addition to the main surface, the portion flowing around to the back side also needs to be sufficiently dried, thus raising concerns about increased drying time. Therefore, it is desirable to minimize the amount of liquid flowing around to the back side before the drying process.

[0038] While the detailed mechanism is not yet determined, it is believed that by appropriately increasing the IPA back angle and / or water back angle, the ease of flow of rinsing liquid on the inclined surface treated with the surface treatment agent composition can be properly controlled. For example, in the case where it is desired to use rotation to shake off rinsing solutions such as IPA and water, the rinsing solution flowing out from the top edge can be well shaken off on the front slope and front shoulder before reaching the edge surface, thus preventing the rinsing solution from going around to the back side via the edge surface.

[0039] The processing method of this embodiment ensures good removal of rinsing liquid from the inclined surface when rinsing the surface of the semiconductor substrate with a water-based or non-aqueous rinsing solution such as an alcohol, primarily based on IPA, after surface treatment. Therefore, it can prevent the rinsing liquid from flowing around to the back of the semiconductor substrate during rotational cleaning, thereby improving manufacturing stability.

[0040] In addition, isopropanol (IPA) and water are sometimes used in the rinsing solution after surface treatment (hereinafter referred to as "second rinsing solution"). The inventors have found that in such embodiments, since the ease of implementation of removing IPA and water is improved, it is desirable that the IPA back angle of the surface treatment agent layer formed by surface treatment is further increased and / or the water back angle of the surface treatment agent layer formed by surface treatment is further increased.

[0041] In addition, in some embodiments, water and IPA are sometimes used as the rinsing solution after surface treatment (hereinafter referred to as "second rinsing solution") to rinse sequentially (e.g., "surface treatment → water rinsing → IPA rinsing", "surface treatment → IPA rinsing → water rinsing", etc.). The inventors have found that in such embodiments, it is desirable for the IPA back angle and the water back angle to be large.

[0042] The IPA recoil angle is 3° or more at room temperature (25°C), preferably 5° or more, more preferably 6° or more, and even more preferably 7° or more; and / or

[0043] The water receding angle is 40° or more at room temperature (25 degrees Celsius), preferably 50° or more, more preferably 60° or more, and even more preferably 70° or more.

[0044] This prevents the rinsing solution from flowing onto the back side of the semiconductor substrate.

[0045] On the other hand, the aforementioned IPA back angle can also be set to, for example, 20° or less, and the aforementioned water back angle can also be set to, for example, 100° or less.

[0046] Furthermore, the standard deviation of the IPA back angle at the specified 10 points on the surface can be configured to be, for example, 5° or less. The difference between the maximum and minimum values ​​of this IPA back angle can be configured to be, for example, 10° or less.

[0047] Similarly, the standard deviation of the water back angle on the surface at the specified 10 locations can, for example, be set to 5° or less. The difference between the maximum and minimum values ​​of this water back angle can, for example, be set to 10° or less.

[0048] Another embodiment of the present invention provides a processing method as follows:

[0049] A processing method for processing the main surface of a semiconductor substrate having a patterned area and a beveled area formed around the periphery of the patterned area, wherein the pattern has a textured structure with a pattern size of 30 nm or less, the method includes the following steps:

[0050] The surface treatment process involves contacting a surface treatment agent composition containing a silylating agent with the aforementioned patterned area and the aforementioned beveled area of ​​the main surface of the aforementioned semiconductor substrate, and

[0051] The evaluation process determines whether the IPA back angle on the main surface of the semiconductor substrate after the aforementioned surface treatment process is 3° or more, and / or

[0052] Is the water receding angle greater than 40°?

[0053] In the evaluation process described above, the IPA back angle and / or water back angle can also be determined by measuring the unpatterned area (non-patterned area) on the main surface.

[0054] In addition, the evaluation process described above can also be judged by measuring the IPA back angle and / or water back angle of a substrate (dummy substrate) having a smooth surface made of the same material as the main surface of the aforementioned semiconductor substrate.

[0055] According to the above method, by including an evaluation step of IPA back angle and / or water back angle in the processing method (measuring the non-patterned area in each substrate treatment or in every certain number of substrate treatments, or measuring the dummy substrate in every certain number of substrate treatments), it can be confirmed whether the surface treatment step of contacting the surface treatment agent composition has been properly performed on each substrate. Therefore, in the event of an abnormality such as the inability to suppress the amount of material wrapped to the back side on a particular substrate when a substrate treated by the processing method of this embodiment occurs, it becomes easy to distinguish whether the cause is that the above-mentioned surface treatment step was not properly performed or the subsequent rinsing process was not properly performed.

[0056] 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 at room temperature (25°C), more preferably 3° or more and 10° or less. This makes it possible to reduce the pattern collapse rate in the patterning region.

[0057] Similarly, the lower limit of the water contact angle on the substrate surface treated with the surface treatment agent composition is preferably 50° or more, more preferably 60° or more, at room temperature of 25 degrees Celsius. This makes it possible to reduce the pattern collapse rate in the pattern forming area. On the other hand, the upper limit of the above-mentioned water contact angle is not particularly limited, and can be, for example, 110° or less at room temperature of 25 degrees Celsius.

[0058] According to this embodiment, by contacting the surface treatment agent composition with the main surface during the surface treatment process, a surface treatment agent layer can be formed on the main surface of the substrate. Therefore, pattern collapse can be suppressed by the surface treatment agent layer on the pattern forming area, and back-side wrapping can be suppressed by the surface treatment agent layer on the beveled area.

[0059] In addition, it is known that during the manufacturing process of forming semiconductor devices on a semiconductor substrate (wafer), foreign matter (particles) such as metal particles and inorganic particles may adhere to the inclined surface at the end of the semiconductor wafer.

[0060] In areas where no pattern is formed and / or on sloped areas, a surface treatment agent layer with the aforementioned IPA back angle and / or water back angle can also be formed to reduce the re-adhesion of foreign matter to sloped areas and areas where no pattern is formed.

[0061] Furthermore, the surface treatment agent composition of this embodiment is used to treat the main surface of a semiconductor substrate having a patterned area and a beveled area formed around the periphery of the patterned area, wherein the pattern has a raised or recessed structure with a pattern size of 30 nm or less.

[0062] Such surface treatment agent compositions contain silylating agents and are configured such that the IPA back angle determined by the following steps is 3° or more at room temperature (25 degrees Celsius) and / or the water back angle determined by the following steps is 40° or more at room temperature (25 degrees Celsius).

[0063] The IPA back angle on the substrate surface treated with the surface treatment agent composition is determined by the following steps.

[0064] A surface treatment agent composition is brought into contact with the surface of a smooth silicon dioxide substrate to perform surface treatment.

[0065] With the substrate in a static position on a horizontal platform, 3 μL of 2-propanol was dropped onto the surface of the surface-treated silica substrate at room temperature (25°C), and the contact angle was measured after 60 seconds. This value was taken as the aforementioned IPA back angle (°).

[0066] Sixty seconds after the droplet is added, the contact angle between the droplet and the substrate is reduced because the 2-propanol has dried. Therefore, the contact angle at this time can be regarded as the IPA back angle.

[0067] In addition, the water receding angle on the substrate surface treated with the surface treatment agent composition is determined by the following steps.

[0068] A surface treatment agent composition is brought into contact with the main surface of a smooth silicon dioxide substrate to perform surface treatment.

[0069] With the substrate placed on a horizontal platform, 30 μL of pure water was added dropwise to the surface of a surface-treated silica substrate at room temperature (25°C). The pure water was then aspirated at a rate of 6 μL / second to reduce the droplet size. The contact angle of the droplets was continuously measured during this process. The contact angle at which the droplet size decreased without any change was taken as the water retreat angle (°).

[0070] The surface of the silicon dioxide substrate is preferably an oxide film, but it may also contain a small amount of unavoidable silicon or other components.

[0071] During the film formation process of the film constituting the semiconductor element in the patterned area, silicon, silicon nitride, and other films mixed with dissimilar materials may sometimes be present in the inclined areas and edge surfaces. In such cases, the rinsing solution can be stably suppressed from flowing around to the back side of the semiconductor substrate by using a surface treatment agent composition that imparts the aforementioned IPA back angle and / or water back angle.

[0072] As the measuring substrate for measuring the IPA back angle and water back angle, a smooth substrate of the same material as the main surface of the semiconductor substrate can also be used. In addition, in the case of a semiconductor substrate with a smooth surface and no patterned area, the same substrate as the semiconductor substrate can be used, that is, the measurement can also be performed in the non-patterned area of ​​the semiconductor substrate.

[0073] In addition, the IPA contact angle or water contact angle of the main surface treated with the surface treatment agent composition is determined by the following steps.

[0074] A surface treatment agent composition is brought into contact with the surface of a smooth silicon dioxide substrate (evaluation substrate) to perform surface treatment.

[0075] With the substrate in a static state on a water platform, 1 μL of 2-propanol or pure water was dropped onto the surface of the surface-treated silica substrate at room temperature (25 degrees Celsius). The contact angle was then measured after 5 seconds and this value was taken as the aforementioned IPA contact angle (°) or water contact angle (°).

[0076] The substrate used for evaluating the IPA contact angle or water contact angle can be used under the same conditions as the IPA back angle or water back angle.

[0077] It should be noted that the above-mentioned steps for measuring the recoil angle and contact angle are typically used to evaluate the properties of surface treatment agent compositions.

[0078] In the evaluation process of the above treatment method, it is acceptable to select any of the following for the measurement temperature of the receding angle and contact angle, any of the following for the droplet volume, and any of the following for the measurement time, which is within 0.1 seconds to 30 seconds after the droplet is added. It is also acceptable to use the above-selected measurement methods for the receding angle and contact angle measurement steps under the measurement conditions.

[0079] In this embodiment, specifically, by appropriately selecting the types and mixing amounts of each component included in the surface treatment agent composition, and the preparation method of the surface treatment agent composition, the IPA receding angle, water receding angle, IPA contact angle, and water contact angle can be controlled. For example, appropriately selecting the type of silylating agent, other components, and preparing the composition immediately after mixing and then using it are considered as requirements for setting the IPA receding angle, water receding angle, IPA contact angle, and water contact angle to a desired numerical range.

[0080] In this specification, "immediately following" or "about to precede" refers to within 24 hours, preferably within 2 hours, and particularly preferably within 30 minutes.

[0081] By using the surface treatment method of the surface treatment agent composition of this embodiment, a method for manufacturing semiconductor substrates with excellent manufacturing manageability and manufacturing stability can be realized.

[0082] (Semiconductor substrate manufacturing method)

[0083] The method for manufacturing the semiconductor substrate according to this embodiment is described in detail below.

[0084] As an example of a method for manufacturing a semiconductor substrate, methods include patterning the main surface of the semiconductor substrate, a pre-rinsing (first rinsing) process, a surface treatment process using a surface treatment agent composition, a post-rinsing (second rinsing) process, a drying process, and removal of the surface treatment agent layer.

[0085] The following uses Figures 1-3 Explain each process step.

[0086] Figure 1 It is a top view viewed from a direction perpendicular to the main surface 12 of the substrate 10 (semiconductor substrate). Figure 2 This is a schematic diagram of a cross-sectional view of the substrate 10 in a specified direction. Figure 3 (a) to Figure 3 (c) is a schematic diagram of a process cross-section in the manufacturing process of a semiconductor substrate.

[0087] First, a substrate 10 with a pattern (convex-concave structure 20) formed on the main surface 12 is prepared.

[0088] In the preparation process of the substrate 10 described above, the following method, which is an example of a method for forming a rough and uneven structure 20 on the surface of the substrate 10, may also be used.

[0089] First, after coating the wafer surface with a photoresist, the photoresist is exposed through a photoresist mask to remove either the exposed or unexposed photoresist, thereby creating a photoresist layer with the desired raised and recessed pattern. Alternatively, a photoresist layer with a raised and recessed pattern can be obtained by pressing a patterned die onto the photoresist. Next, the wafer is etched. At this time, the substrate surface corresponding to the recessed portions of the photoresist pattern is selectively etched. Finally, if the photoresist layer is peeled off, a wafer (substrate 10) with a raised and recessed structure 20 on its surface is obtained.

[0090] There are no particular restrictions on the wafer with the uneven structure 20 and the material of the uneven structure 20.

[0091] As a material for wafers, various types of wafers can be used, such as silicon wafers, silicon carbide wafers, wafers composed of multiple components containing silicon, sapphire wafers, and various compound semiconductor wafers.

[0092] The material of the uneven structure 20 may include one or more of the following: oxides, nitrides, oxynitrides, carbonitrides, and carbon oxides composed of Si, Ti, Ge, W, and Ru. For example, silicon-based materials such as silicon oxide, silicon nitride, polycrystalline silicon, monocrystalline silicon, and silicon-germanium, metal-based materials such as titanium nitride, tungsten, ruthenium, tantalum nitride, and tin, as well as materials combining these, and photoresist materials may be used as the material of the uneven structure 20.

[0093] Figure 1 The substrate 10 has a patterned area 30 with a pattern (convex-concave structure 20) and a patternless area 32 without a pattern on its main surface 12. It should be noted that the substrate can also be processed as a substrate without a patternless area.

[0094] Figure 1 The substrate 10 may also have a notch 14 formed on a portion of its periphery. The notch 14 may also have a straight cut, called an orientation plane, indicating the direction of the crystal axis, or a V-shaped cut, called a notch, to determine its position in an exposure apparatus or the like.

[0095] The pattern forming region 30 is the region in which one or more uneven structures 20 are formed when viewed from a direction perpendicular to the main surface 12, i.e., in top view. The pattern forming region 30 may also include a device forming region in which one or more semiconductor devices are formed.

[0096] The uneven structure 20 can, for example, be composed of a three-dimensional structure having "one or more structures arranged in a vertical direction along the main surface 12" and / or "one or more structures arranged in a horizontal direction orthogonal to the vertical direction". As an example of such a three-dimensional structure, it can also constitute at least part of a logic device or a memory, such as FinFET, nanowire FET, nanosheet FET or other multi-gate FET, three-dimensional memory cell, etc.

[0097] The unformed pattern area 32 is an area formed in top view of at least a portion or the entire periphery of the pattern-forming area 30. The unformed pattern areas 32 may be formed continuously with each other or may be divided into multiple areas.

[0098] At least a portion of the unpatterned area 32 has a smooth surface area where the uneven structure 20 is not formed.

[0099] One or more cutting areas for cutting can also be formed in the pattern forming area 30 and / or between the pattern forming area 30 and the unformed pattern area 32.

[0100] Figure 2 This is a cross-sectional view showing an example of the concave-convex structure 20.

[0101] In this embodiment, the pattern size of the convex-concave structure 20 can be defined as the size in at least one width direction in the in-plane direction of the main surface 12, and / or the size in at least one height direction in the direction perpendicular to the main surface 12.

[0102] In the cross-sectional structure (in the substrate thickness direction) of the pattern of the uneven structure 20, at least one of the pattern dimensions of width and height, or in the three-dimensional structure (three-dimensional coordinates of XYZ) of the pattern of the uneven structure 20, at least one of the pattern dimensions of width (length in the X-axis direction), height (length in the Y-axis direction), and depth (length in the Z-axis direction), can be, for example, less than 30 nm, less than 20 nm, or less than 10 nm. It can also be the spacing between patterns. When using a substrate 10 having such a fine uneven structure 20, the surface treatment agent composition of this embodiment can also be applied.

[0103] Such a surface treatment agent composition is suitable for surface treatment of a substrate 10 having a textured structure 20, wherein the pattern size of the textured structure 20 is, for example, 30 nm or less, preferably 20 nm or less.

[0104] Specifically, the aspect ratio of the protrusion 22 can be 3 or more, 5 or more, or 10 or more. Even in the concave-convex structure 20 of the protrusion 22, which has a fragile structure, pattern collapse can be suppressed.

[0105] On the other hand, the aspect ratio of the protrusion 22 is not particularly limited and can be less than 100.

[0106] The aspect ratio of the protrusion 22 is shown by dividing the height of the protrusion 22 by the width of the protrusion 22.

[0107] Substrate 10 Figure 1 , 2 As shown, a sloped region 50 may also be formed at least a portion of the end of the substrate 10. The sloped region 50 may be any sloped surface formed on the main surface 12, specifically, it may have a top edge 51, an upper slope 52, a front shoulder 53, an edge surface 54, and a lower slope 55.

[0108] Next, the main surface 12 of the substrate 10 may be brought into contact with an aqueous cleaning solution (cleaning process) as needed.

[0109] Examples of aqueous cleaning solutions include water, alcohol, aqueous solutions of ammonium hydroxide, aqueous solutions of tetramethylammonium, aqueous solutions of hydrochloric acid, aqueous solutions of hydrogen peroxide, aqueous solutions of sulfuric acid, and organic solvents. These can be used alone or in combination of two or more.

[0110] The cleaning process may be performed once or twice or more before the surface treatment process and before the first rinsing process. Other processes may also be included between multiple cleaning processes or between the cleaning process and the surface treatment process.

[0111] Next, the main surface 12 of the substrate 10 may be brought into contact with the first rinsing solution (first rinsing step) as needed. As the first rinsing solution, a cleaning liquid different from an aqueous cleaning solution may be used, such as water, organic solvents, mixtures thereof, or those containing at least one of an acid, alkali, surfactant, or oxidant.

[0112] Examples of organic solvents used in the first rinsing solution include: hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, alcohols, derivatives of polyols, and nitrogen-containing solvents. Preferably, at least one alcohol selected from methanol, 1-propanol, and 2-propanol (isopropanol), which have 3 or fewer carbon atoms, is used as the organic solvent.

[0113] Alternatively, multiple solutions can be used as the first rinsing solution. For example, rinsing can be performed in the order of solution containing acidic or alkaline aqueous solution → organic solvent. Additionally, an aqueous cleaning solution can optionally be added further, in the order of solution containing acidic or alkaline aqueous solution → aqueous cleaning solution → organic solvent.

[0114] The first rinsing step can be performed once or twice or more after the cleaning step and before the surface treatment step. Other steps may also be included between multiple first rinsing steps or between the first rinsing step and the surface treatment step.

[0115] Next, as Figure 3 As shown in (a), the surface treatment agent composition 60 of this embodiment is brought into contact with the main surface 12 (surface treatment agent composition) of the substrate 10.

[0116] Preferably, the surface treatment agent composition 60, which is a liquid, is supplied to the uneven structure 20 formed on the surface of the substrate 10. In this case, it may also be supplied in a manner that fills part or all of the recesses 24 of the uneven structure 20.

[0117] The surface treatment agent composition 60 can also be supplied while the first rinsing solution and aqueous cleaning solution are still present on the main surface 12. That is, by replacing the first rinsing solution and aqueous cleaning solution with the surface treatment agent composition 60, the surface treatment process can be performed before the surface of the uneven structure 20 on the main surface 12 of the substrate 10 becomes dry.

[0118] The surface treatment agent composition 60 can be supplied by a single-wafer method, such as a spin coating method, in which the composition is supplied to the vicinity of the rotation center while the wafers are rotated almost horizontally to replace the cleaning liquid or the like that held in the pattern of the wafers, thereby filling the composition.

[0119] Next, as Figure 3 As shown in (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.

[0120] Alternatively, as needed, known methods such as heating, depressurization, and drying can be applied to the surface treatment agent composition 60 on the main surface 12 to promote the formation of the surface treatment agent layer 70.

[0121] The surface treatment agent layer 70 is formed on the main surface 12 of the substrate 10 in the pattern forming region 30 and the slope region 50. It can also be formed in the unpatterned region 32 if the substrate 10 has a patterned unpatterned region 32. Alternatively, the surface treatment agent layer 70 can also be formed on the edge surface 54 and the lower slope surface 55.

[0122] Next, the main surface 12 on which the surface treatment agent layer 70 is formed may be brought into contact with the second rinsing liquid (second rinsing process) as needed.

[0123] As a second rinsing solution, the example shown in the first rinsing solution can be used.

[0124] Alternatively, various solutions can be used as the second rinsing solution. For example, rinsing can be performed in the order of water → organic solvents such as isopropanol.

[0125] The second rinsing process may be performed once or more after the surface treatment process. Other processes may also be included between multiple second rinsing processes or between the second rinsing process and the surface treatment process.

[0126] Next, a drying process to dry the main surface 12 of the substrate 10 can be performed as needed.

[0127] The liquid present on the main surface 12 of the substrate 10 can be removed through the drying process.

[0128] As a drying method, known methods such as rotary drying, IPA (2-propanol) steam drying, Marangoni drying, heating drying, hot air drying, and vacuum drying can also be used.

[0129] The drying process can be performed once or more, for example, after the surface treatment process and after the second rinsing process. It should be noted that the drying process and the second rinsing process can also be repeated alternately.

[0130] Next, as Figure 3 As shown in (c), the surface treatment agent layer 70 on the main surface 12 of the substrate 10 can also be removed (removal process).

[0131] Examples of removal methods include heating, UV irradiation, ozone exposure, plasma irradiation, and corona discharge. Additionally, treatment using concentrated fluids such as supercritical fluids (which may contain acids, alkalis, or oxidants) or steam treatment can also be performed. These methods can be used individually or in combination. These treatments can also be carried out under atmospheric pressure or reduced pressure.

[0132] Based on the above, a semiconductor substrate (substrate 10) using the surface treatment agent composition of this embodiment can be obtained.

[0133] like Figure 3 The manufacturing method shown uses a wafer pattern as the object, but the present invention is not limited thereto. In the substrate manufacturing method of this embodiment, by using the surface treatment agent composition of the present invention in the cleaning and drying processes of the resist pattern, the collapse of the resist pattern can also be suppressed.

[0134] The above-described supply process describes a manufacturing method implemented after the cleaning process, but it is not limited to this; it can also be implemented after various treatments performed on the uneven structure 20.

[0135] In addition to the steps described above, the substrate manufacturing method may also combine one or more known processes. For example, surface treatments such as plasma treatment may be performed after the removal steps described above.

[0136] Next, the surface treatment agent composition used in the surface treatment of the semiconductor substrate described above will be explained.

[0137] The surface treatment agent composition of this embodiment contains a silylating agent.

[0138] The aforementioned silylating agent can be any known silylating agent. As a silylating agent, a silicide represented by, for example, the general formula [1] below can be used. These can be used alone or in combination of two or more.

[0139] R 1 a Si(H) b X 4-a-b [1]

[0140] In the above general formula [1], R 1 Each of the following is an organic group consisting of a hydrocarbon group with 1 to 18 carbon atoms, which contains some or all of the hydrogen atoms and is optionally replaced by fluorine. Each of the following is an organic group consisting of a monovalent organic group bonded to the Si element, which is nitrogen, oxygen, carbon, or halogen. a is an integer from 1 to 3, b is an integer from 0 to 2, and the sum of a and b is 1 to 3.

[0141] In the above general formula [1], R 1 It contains not only hydrogen, carbon, nitrogen, oxygen, and fluorine, but also silicon, sulfur, and halogen elements (other than fluorine).

[0142] In addition, R in the above general formula [1] 1 It can also contain unsaturated bonds, aromatic rings, and cyclic structures.

[0143] R in the above general formula [1] 1 , can be listed as each independently selected from C e H 2e+1 (e = 1–18) and C f F 2f+1 At least one group in CH2CH2 (f = 1 to 8). A silicide having a trialkylsilyl group may be used.

[0144] It should be noted that R in the above general formula [1]1 When silicon is included, the structure of the general formula [1-1] shown below can also be adopted.

[0145] R 1 m X 3-m-n (H) n Si-(CH2) p -Si(H) n X 3-m-n R 1 m [1-1]

[0146] It should be noted that in the above general formula [1-1], R 1 (wherein, the R) 1 (The formula does not contain silicon) and X are the same as the above general formula [1], m is an integer from 1 to 2, n is an integer from 0 to 1, the sum of m and n is 1 to 2, p is an integer from 1 to 18, and the methylene chain represented by -(CH2)p- is optionally replaced by a halogen.

[0147] In the X of the above general formula [1], the monovalent organic groups bonded to the Si element are not only hydrogen, carbon, nitrogen, and oxygen elements, but may also include silicon, sulfur, halogen elements, etc.

[0148] Examples of monovalent organic groups that bond with Si and are nitrogen-containing include: isocyanate groups, amino groups, dialkylamino groups, isothiocyanate groups, azide groups, acetamido groups, -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, imidazole rings, triazole rings, tetraazole rings, oxazolidinone rings, morpholine rings, -NH-C(=O)-Si(CH3)3, -N(S(=O)2R 4 )2(Here, R 4 Each of the following groups is independently selected from the group consisting of a monovalent hydrocarbon group with 1 to 8 carbon atoms, which is selected from some or all of the hydrogen elements and optionally replaced by fluorine, and a substituent having the structure of the following general formula [1-2].

[0149]

[0150] (In the above general formula [1-2], R) 5 Each of the following groups is a divalent hydrocarbon group consisting of 1 to 8 carbon atoms, which are independently, partially or entirely replaced by fluorine. (N=C(NR)) 62 2. -N = C(NR)62 )R 6 (Here, R) 6 The groups are independently selected from hydrogen groups, -C≡N groups, -NO₂ groups, and hydrocarbon groups whose hydrogen elements are optionally substituted with fluorine. These hydrocarbon groups may also have oxygen and / or nitrogen atoms. ( ), -N(R a1 (R) a2 (Here, the above R) a1 R represents a hydrogen atom or a saturated or unsaturated alkyl group. a2 Indicates saturated or unsaturated alkyl, saturated or unsaturated cycloalkyl, or saturated or unsaturated heterocycloalkyl. R a1 and R a2 They can also bond with each other to form saturated or unsaturated heterocyclic alkyl groups with nitrogen atoms. a3 )-Si(R a4 (R) a5 (R) a6 (Here, the above R) a3 Represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a trimethylsilyl group, or a dimethylsilyl group, wherein the above R a4 R a5 and R a6 Each can independently represent a hydrogen atom or an organic group, R a4 R a5 and R a6 It contains a total of one or more carbon atoms. a7 )-C(=O)R a8 (Here, the above R) a7 R represents hydrogen atom, methyl, trimethylsilyl or dimethylsilyl. a8 This indicates a hydrogen atom, saturated or unsaturated alkyl group, fluorinated alkyl group, or trialkylsilylamino group, etc.

[0151] As a silylating agent in the above general formula [1] where X is a monovalent organic group of nitrogen bonded to Si, examples include CH3Si(NH2)3, C2H5Si(NH2)3, C3H7Si(NH2)3, C4H9Si(NH2)3, and C5H 11 Si(NH2)3, C6H 13 Si(NH2)3, C7H 15 Si(NH2)3, C8H 17 Si(NH2)3, C9H 19 Si(NH2)3, C 10 H 21 Si(NH2)3, C 11 H 23 Si(NH2)3, C 12 H25 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 37Si(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 11 Si(CH3)2NH2、C6H 13 Si(CH3)2NH2、C7H 15 Si(CH3)2NH2、C8H 17 Si(CH3)2NH2、C9H 19 Si(CH3)2NH2、C 10 H 21 Si(CH3)2NH2、C 11 H 23 Si(CH3)2NH2、C 12 H 25 Si(CH3)2NH2、C 13 H 27 Si(CH3)2NH2、C 14 H 29 Si(CH3)2NH2、C 15 H 31 Si(CH3)2NH2、C 16 H 33 Si(CH3)2NH2、C 17 H 35 Si(CH3)2NH2、C 18 H 37 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 11 CH2CH2Si(NH2)3, C6F 13 CH2CH2Si(NH2)3, C7F 15 CH2CH2Si(NH2)3, C8F 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、C6F 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, C6F 13 CH2CH2Si(CH3)2NH2、C7F 15 CH2CH2Si(CH3)2NH2, C8F 17 The aminosilanes such as CH2CH2Si(CH3)2NH2, CF3CH2CH2Si(CH3)(H)NH2, aminodimethylvinylsilane, aminodimethylphenylethylsilane, aminodimethylphenylsilane, aminomethyldiphenylsilane, and aminodimethyltert-butylsilane, or aminosilanes in which the amino group (-NH2 group) is replaced with -N=C=O, dialkylamino (-N(CH3)2, -N(C2H5)2, etc.), tert-butylamino, allylamino, -N=C=S, -N3, -NHC(=O)CH3, -NHC(=O)CF3, and -N(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), imidazole ring (e.g., N-trimethylsilylimidazolium), triazole ring (e.g., N-trimethylsilyltriazole), tetrazolium ring, oxazolidinone ring, morpholine ring, -NH-C(=O)-Si(CH3)3, -N(S(=O)2R 4 )2(Here, R 4Each group is independently selected from the group consisting of a monovalent hydrocarbon group with 1 to 8 carbon atoms, chosen from some or all of the hydrogen elements and optionally replaced by fluorine, and a fluorine element. Examples include N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide, etc., and substituents adopting the structures of the following general formulas [1-2].

[0152]

[0153] (In the above general formula [1-2], R) 5 Each of the following is an independent divalent hydrocarbon group, consisting of one or all of the hydrogen atoms, which may be substituted with fluorine. Examples include N-(trimethylsilyl)-N,N-difluoromethane-1,3-di(sulfonyl)imide, etc., and -N=C(NR) 62 2. -N = C(NR) 62 )R 6 (Here, R) 6 The hydrocarbon groups are independently selected from hydrogen groups, -C≡N groups, -NO₂ groups, and hydrocarbon groups in which some or all of the hydrogen elements are optionally replaced by fluorine elements. These hydrocarbon groups may also have oxygen and / or nitrogen atoms. Examples include 2-trimethylsilyl-1,1,3,3-tetramethylguanidine, etc., and -N(R a1 )R a2 (Here, the above R) a1 R represents a hydrogen atom or a saturated or unsaturated alkyl group. a2 Indicates saturated or unsaturated alkyl, saturated or unsaturated cycloalkyl, or saturated or unsaturated heterocycloalkyl. R a1 and R a2 They can also bond with each other to form saturated or unsaturated heterocyclic alkyl groups with nitrogen atoms. a3 )-Si(R a4 (R) a5 (R) a6 (Here, the above R) a3 Represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a trimethylsilyl group, or a dimethylsilyl group, wherein the above R a4 R a5 and R a6 Each can independently represent a hydrogen atom or an organic group, R a4 R a5 and R a6It contains a total of one or more carbon atoms. Examples include hexamethyldisilazane, N-methylhexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-dimethyldisilazane, 1,3-di-N-octyltetramethyldisilazane, 1,3-divinyltetramethyldisilazane, heptamethyldisilazane, N-allyl-N,N-bis(trimethylsilyl)amine, 1,3-diphenyltetramethyldisilazane, and 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, nonamethyltrisilazane, pentamethylethyldisilazane, pentamethylvinyldisilazane, pentamethylpropyldisilazane, pentamethylethyldisilazane, pentamethyltert-butyldisilazane, pentamethylphenyldisilazane, trimethyltriethyldisilazane, etc. a7 )-C(=O)R a8 (Here, the above R) a7 R represents hydrogen atom, methyl, trimethylsilyl or dimethylsilyl. a8 This indicates a hydrogen atom, saturated or unsaturated alkyl group, fluorinated alkyl group, or trialkylsilylamino group. Examples include N-trimethylsilylacetamide, N-trimethylsilyltrifluoroacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bis(trimethylsilyl)acetamide, bis(trimethylsilyl)trifluoroacetamide, etc.

[0154] As a silylating agent in the above general formula [1] where X is a monovalent organic group bonded to the Si element and is oxygen, for example, replacing the amino group (-NH2 group) of the above aminosilane with -OC (=A)R a9 (Here, A represents O and CHR) a10 CHOR a10 CR a10 R a10 or NR a11 R a9 R a10 Each of the above independently represents a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a fluorinated alkyl group, a chloroalkyl group, a trialkylsilyl group, a trialkylsiloxy group, an alkoxy group, a phenyl group, a phenylethyl group, or an acetyl group. a11 This indicates a hydrogen atom, alkyl group, or 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 (Here, the above R) a12R represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorinated alkyl group, or a trialkylsilylamino group. a13 This indicates a hydrogen atom, alkyl group, trialkylsilyl group, or -OC(R). a14 )=CH-C(=O)R a15 (Here, the above R) a14 and R a15 Each can independently represent a hydrogen atom or an organic group. Examples include trimethylsilyloxy-3-penten-2-one and 2-trimethylsilyloxy-penten-4-one. a16 (Here, the above R) a16 This indicates saturated or unsaturated alkyl groups, saturated or unsaturated cycloalkyl groups, and fluorinated alkyl groups. Examples include CH3Si(OCH3)3, C2H5Si(OCH3)3, C3H7Si(OCH3)3, C4H9Si(OCH3)3, and 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 H 25 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 15Si(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 37 Si(CH3)(OCH3)2、(CH3)3SiOCH3、C2H5Si(CH3)2OCH3、(C2H5)2Si(CH3)OCH3、(C2H5)3SiOCH3、C3H 7Si(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、C16 H 33 Si(CH3)2OCH3, C 17 H 35 Si(CH3)2OCH3, C 18 H 37 Si(CH3)2OCH3, (CH3)2Si(H)OCH3, CH3Si(H)2OCH3, (C2H5)2Si(H)OCH3, C2H5Si(H)2OCH3, C2H5Si(CH3)(H)OCH3, (C3H7)2 Si(H)OCH3, or CF3CH2CH2Si(OCH3)3, C2F5CH2CH2Si(OCH3)3, C3F7CH2CH2Si(OCH3)3, C4F9CH2CH2Si(OCH3)3, C5F 11 CH2CH2Si(OCH3)3, CF 13 CH2CH2Si(OCH3)3, C7F 15 CH2CH2Si(OCH3)3, C8F 17 CH2CH2Si(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, C8F 17Fluoroalkyl methoxysilanes such as CH2CH2Si(CH3)2OCH3 and CF3CH2CH2Si(CH3)(H)OCH, or compounds in which the methyl portion of the methoxy group of the above methoxysilane is replaced by one or all of the hydrogen atoms, optionally substituted with fluorine, and consisting of a monovalent hydrocarbon group having 2 to 18 carbon atoms. (e.g., -OS(=O)2-R) a17 (Here, the above R) a17 This refers to alkyl, perfluoroalkyl, phenyl, tolyl, and -O-Si(CH3)3 groups having 1 to 6 carbon atoms. Examples include trimethylsilyl sulfonate, trimethylsilyl benzenesulfonate, trimethylsilyl toluenesulfonate, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl perfluorobutyrate, bis(trimethylsilyl)sulfate, etc., and -OP(-O-Si(CH3)3)2 (e.g., tri(trimethylsilyl) phosphite, etc.).

[0155] In addition, as a silylating agent in the above general formula [1] where X is a monovalent organic group bonded to Si and the element is oxygen, examples include: hexamethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,1-triethyl-3,3-dimethyldisiloxane, 1,1,3,3-tetraoctyldimethyldisiloxane, bis(nonafluorohexyl)tetramethyldisiloxane, 1,3-bis(trifluoropropyl)tetramethyldisiloxane, 1,3-di-n-butyltetramethyldisiloxane, 1,3-di-n-octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, hexamethyldisiloxane, and hexamethyldisiloxane. 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, 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(tert-butyl)disiloxane, vinyl-1,1,3,3-tetramethyldisiloxane Siloxanes, 1,1,1-trimethyl-3,3,3-triphenyldisiloxane, 3,3-diphenyltetramethyltrisiloxane, 3-phenylheptamethyltrisiloxane, 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-Hepanomethyltrisiloxane, 1,1,3,3,5,5-Hexamethyltrisiloxane, 1,1,1,5,5,5-Hexaethyl-3-methyltrisiloxane, furfuryloxytrisiloxane, tetra(dimethylsiloxy)silane, 1,1,3,3,5,5,7,7-Octamethyltetrasiloxane, diphenylsiloxane-dimethylsiloxane copolymer, 1,3-Diphenyl-1,3-Dimethyldisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(trimethylsiloxy)-1,Siloxane compounds include 3-dimethyldisiloxane, tetra-n-propyltetramethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, decamethyltetrasiloxane, dodecylcyclohexasiloxane, dodecylpentasiloxane, tetradecylmethylhexasiloxane, hexaphenylcyclotrisiloxane, polydimethylsiloxane, polyoctadecylmethylsiloxane, decamethylcyclopentasiloxane, poly(3,3,3-trifluoropropylmethylsiloxane), trimethylsiloxy-terminated polydimethylsiloxane, and 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane.

[0156] As a silylating agent in the above general formula [1] where X is a monovalent organic group bonded to Si, for example, replacing the amino group (-NH2 group) of the above aminosilane with -C(S(=O)2R 7 )3(Here, R 7 Each group is independently selected from the group consisting of a monovalent hydrocarbon group with 1 to 8 carbon atoms, in which some or all of the hydrogen elements are substituted with fluorine, and a fluorine element. Examples include (trimethylsilyl)tri(trifluoromethanesulfonyl)methyl compounds, etc.

[0157] In addition, as a silylating agent in the above general formula [1] where X is a halogenated organic group bonded to the Si element, for example, the amino group (-NH2 group) of the above aminosilane can be replaced with a chlorine group, a bromine group, or an iodine group (e.g., chlorotrimethylsilane, bromotrimethylsilane, etc.).

[0158] As the aforementioned silylating agent, it may contain cyclic silazane compounds.

[0159] Examples of the aforementioned cyclic silazane compounds include: cyclic disilazane compounds such as 2,2,5,5-tetramethyl-2,5-disil-1-azacyclopentane and 2,2,6,6-tetramethyl-2,6-disil-1-azacyclohexane; cyclic trisilazane compounds such as 2,2,4,4,6,6-hexamethylcyclotrisilazane and 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane; cyclic tetrasilazane compounds such as 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane; and so on.

[0160] In addition to the silylating agent described above, the surface treatment agent composition may also contain one or more catalysts selected from the group consisting of compound A (described later), imides, nitrogen-containing compounds, nitrogen-containing heterocyclic compounds without silicon atoms, and silylating heterocyclic compounds as silylating agents. Here, a catalyst refers to a catalyst that promotes the reaction between the main surface and the silylating agent, thereby improving the water-repellent properties of the formed surface treatment agent layer; the catalyst itself or a modified catalyst may also constitute part of the surface treatment agent layer.

[0161] The concentration of the catalyst relative to 100% by mass of the surface treatment agent composition 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.

[0162] Specific examples of compound A include trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyl dimethylsilyl trifluoroacetate, butyl dimethylsilyl trifluoromethanesulfonate, hexyl dimethylsilyl trifluoroacetate, hexyl dimethylsilyl trifluoromethanesulfonate, octyl dimethylsilyl trifluoroacetate, octyl dimethylsilyl trifluoromethanesulfonate, decyl dimethylsilyl trifluoroacetate, and decyl dimethylsilyl trifluoromethanesulfonate, and may include one or more selected from these. These can be used alone or in combination of two or more.

[0163] It should be noted that there are also compounds A that meet the criteria for the silylating agents mentioned above, but when used as a catalyst, this refers to their combination with other silylating agents besides compound A.

[0164] The above-mentioned compound A can also be formed by reacting a silicide 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.

[0165] The remaining silicon compound represented by the following general formula [2] that is not consumed in the reaction can be used as the silylating agent mentioned above together with compound A obtained in the reaction. The silicide represented by the following general formula [2] can also be reacted at a molar ratio of, for example, 0.2 to 100,000 molar times relative to the above acetic acid or sulfonic acid, preferably 0.5 to 50,000 molar times, more preferably 1 to 10,000 molar times.

[0166] R 2 c (H) d Si-X[2]

[0167] In the above general formula [2], R is used as 2 c(H)dSi- can be listed as: (CH3)3Si-, (CH3)2(H)Si-, (C4H9)(CH3)2Si-, (C6H 13 (CH3)2Si-, (C8H 17 (CH3)2Si-, (C 10 H 21 )(CH3)2Si- etc. In addition, X is the same as the above general formula [1].

[0168] In addition, the above-mentioned compound A may also be selected from at least one of the following groups: sulfonic acid represented by the following general formula [3], acid anhydride of the sulfonic acid, salt of the sulfonic acid, and sulfonic acid derivatives represented by the following general formula [4].

[0169] R 8 -S(=O)2OH[3]

[0170] In the above general formula [3], R 8 The group selected is composed of a monovalent hydrocarbon group with 1 to 8 carbon atoms, substituted with fluorine, and a hydroxyl group, with some or all of the hydrogen elements chosen.

[0171] R 8’ -S(=O)2O-Si(H) 3-r (R 9 ) r [4]

[0172] In the above general formula [4], R 8’ R is a monovalent hydrocarbon group with 1 to 8 carbon atoms, in which some or all of the hydrogen element is optionally replaced by fluorine. 9 Each group is independently selected from at least one monovalent hydrocarbon group consisting of 1 to 18 carbon atoms, chosen from some or all of the hydrogen atoms and optionally substituted with fluorine, where r is an integer from 1 to 3.

[0173] In addition, the above-mentioned compound A may also be at least one of the following groups: sulfonate esters represented by the following general formula [5], sulfonamides represented by the following general formulas [6] and [7], sulfonamide derivatives represented by the following general formulas [8] and [9], sulfonyl methyl compounds represented by the following general formula

[10] , and sulfonyl methyl compound derivatives represented by the following general formula

[11] .

[0174] R 10 -S(=O)2OR 11 [5]

[0175] In the above general formula [5], R 10 To select groups from the group consisting of a monovalent hydrocarbon group with 1 to 8 carbon atoms that is substituted by fluorine, and a fluorine element, R 11 It is a monovalent alkyl group having 1 to 18 carbon atoms.

[0176] (R 12 -S(=O)2)2NH[6]

[0177] In the above general formula [6], R 12 Each of these groups is independently selected from the group consisting of a monovalent hydrocarbon group (1-8 carbons) chosen from some or all of the hydrogen elements, optionally substituted with fluorine, and a fluorine element.

[0178]

[0179] In the above general formula [7], R 13 [A divalent hydrocarbon group consisting of 1 to 8 carbon atoms, with some or all of the hydrogen atoms optionally replaced by fluorine.]

[0180] ((R 14 -S(=O)2)2N) s Si(H) t (R 15 ) 4-s-t [8]

[0181] In the above general formula [8], R 14 R is a group independently selected from the group consisting of a monovalent hydrocarbon group with 1 to 8 carbon atoms, which is substituted by fluorine, and a fluorine element, with some or all of the hydrogen elements being chosen. 15 Each of the following groups consists of monovalent hydrocarbon groups with 1 to 18 carbon atoms, each independently having some or all of its hydrogen atoms substituted by fluorine; s is an integer from 1 to 3; t is an integer from 0 to 2; and the sum of s and t is less than 3.

[0182]

[0183] In the above general formula [9], R 16 R are divalent hydrocarbon groups with 1 to 8 carbon atoms, each independently consisting of some or all of the hydrogen element, which are optionally replaced by fluorine. 17 Each of the following groups consists of monovalent hydrocarbon groups with 1 to 18 carbon atoms, each independently having some or all of the hydrogen atoms optionally replaced by fluorine; u is an integer from 1 to 3; v is an integer from 0 to 2; and the sum of u and v is less than 3.

[0184] (R 18 -S(=O)2)3CH

[10]

[0185] In the above general formula

[10] , R 18 Each of these groups is independently selected from the group consisting of a monovalent hydrocarbon group (1-8 carbons) chosen from some or all of the hydrogen elements, optionally substituted with fluorine, and a fluorine element.

[0186] ((R 19 -S(=O)2)3C) w Si(H) x (R 20 ) 4-w-x

[11]

[0187] In the above general formula

[11] , R 19R is a group independently selected from the group consisting of a monovalent hydrocarbon group with 1 to 8 carbon atoms, which is substituted by fluorine, and a fluorine element, with some or all of the hydrogen elements being chosen. 20 Each of the following groups consists of monovalent hydrocarbon groups with 1 to 18 carbon atoms, each independently having some or all of its hydrogen atom substituted with fluorine; w is an integer from 1 to 3; x is an integer from 0 to 2; and the sum of w and x is 3 or less.

[0188] In addition, examples of the aforementioned imides include compounds having a chemical structure formed by imidizing acids such as carboxylic acids and phosphoric acids.

[0189] In addition, at least one of the compounds represented by the following general formulas

[12] and

[13] can be listed as nitrogen-containing compounds.

[0190] R 21 -N=C(NR 22 2)2

[12]

[0191] R 21 -N=C(NR 22 2)R 22

[13]

[0192] In the above general formulas

[12] and

[13] , R 21 The hydrocarbon group is selected from hydrogen-based, -C≡N-based, -NO₂-based, alkylsilyl-based, and hydrocarbon groups in which some or all of the hydrogen elements are optionally replaced by fluorine. The hydrocarbon group may also have oxygen and / or nitrogen atoms, but if nitrogen atoms are included, it shall be a non-cyclic structure. R 22 The hydrocarbon groups are independently selected from hydrogen groups, -C≡N groups, -NO₂ groups, and hydrocarbon groups in which some or all of the hydrogen elements are optionally replaced by fluorine elements. These hydrocarbon groups may also have oxygen and / or nitrogen atoms, but if nitrogen atoms are included, they must be non-cyclic structures.

[0193] In addition, examples of the nitrogen-containing compounds mentioned above 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-pentafluoropropanediamine.

[0194] In addition, at least one of the compounds represented by the following general formulas

[14] and

[15] can be listed as the above-mentioned nitrogen-containing heterocyclic compounds and silylated heterocyclic compounds that do not contain silicon atoms.

[0195]

[0196] In the above general formula

[14] , R 23 and R 24Each group is an independent divalent organic group formed by carbon and / or nitrogen and hydrogen, with a total number of carbons and nitrogens ranging from 1 to 9. In cases where the number of carbons is greater than 2, carbons that do not form a ring may also be present.

[0197]

[0198] In the above general formula

[15] , R 25 The following are alkyl groups having 1 to 6 carbon atoms whose hydrogen atoms are optionally substituted with fluorine: trialkylsilyl groups having 1 to 8 carbon atoms whose hydrogen atoms are optionally substituted with fluorine; alkenyl groups having 2 to 6 carbon atoms whose hydrogen atoms are optionally substituted with fluorine; alkoxy groups having 1 to 6 carbon atoms whose hydrogen atoms are optionally substituted with fluorine; amino groups having 1 to 6 carbon atoms whose hydrogen atoms are optionally substituted with fluorine; alkylamino groups having 1 to 6 carbon atoms whose hydrogen atoms are optionally substituted with fluorine; dialkylamino groups having 1 to 6 carbon atoms whose hydrogen atoms are optionally substituted with fluorine; aminoalkyl groups having 1 to 6 carbon atoms whose hydrogen atoms are optionally substituted with fluorine; nitro, cyano, phenyl, benzyl, or halogroup; R 26 R 27 and R 28 Alkyl or hydrogen groups having 1 to 6 carbon atoms, which may be individually or independently substituted with fluorine, for some or all of the hydrogen atoms.

[0199] Furthermore, the aforementioned nitrogen-containing heterocyclic compounds that do not contain silicon atoms may also contain heteroatoms other than nitrogen atoms, such as oxygen atoms and sulfur atoms, and may also be aromatic. They may also be compounds in which two or more rings are bonded together by single bonds or polyvalent linkages with two or more valences. In addition, they may also contain substituents.

[0200] Examples of nitrogen-containing heterocyclic compounds that do not contain silicon atoms include pyridine, pyrazine, pyrazine, pyrimidine, triazine, tetrazine, pyrrole, pyrazole, imidazole, triazole, tetraazole, oxazole, isoxazole, thiazole, isothiazole, oxadiazole, thiadiazole, quinoline, isoquinoline, cyclophosphine, phthalazine, quinoxaline, quinazoline, indole, indazole, benzimidazole, benzotriazole, benzoxazole, benziisoxazole, benzothiazole, benziisothiazole, benzoxadiazole, benzothiadiazole, saccharin, pyrrolidine, and piperidine.

[0201] In addition, examples of the aforementioned silylated heterocyclic compounds include: silylated imidazole compounds and silylated triazole compounds. Examples of silylated heterocyclic compounds include: monomethylsilylimidazolium, dimethylsilylimidazolium, trimethylsilylimidazolium, monomethylsilyltriazole, dimethylsilyltriazole, and trimethylsilyltriazole.

[0202] It should be noted that some of the aforementioned silylated heterocyclic compounds also conform to the above-mentioned silylating agents, but when used as catalysts, they refer to being used in combination with other silylating agents besides silylated heterocyclic compounds.

[0203] In the above surface treatment agent composition, the concentration of the silylating agent and the total concentration of the silylating agent and the catalyst, relative to 100% by mass of the above surface treatment agent composition, can 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.

[0204] Surface treatment agent compositions may contain solvents.

[0205] There are no particular limitations on the solvents used, as long as they can dissolve the silylating agent. Examples of solvents that can be used include: hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, alcohols, carbonate solvents, polyol derivatives, nitrogen-containing solvents, organosilicon solvents, and thiols. Among these, hydrocarbons, esters, ethers, halogen-containing solvents, sulfoxide solvents, and polyol derivatives that do not contain an OH group are preferred.

[0206] These can be used individually or in combination of two or more.

[0207] Examples of the aforementioned hydrocarbons include: linear, branched, or cyclic hydrocarbon solvents, aromatic hydrocarbon solvents, terpene solvents, etc., such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane, and branched hydrocarbons with corresponding carbon numbers (e.g., isododecane, isohexadecane, etc.), cyclohexane, methylcyclohexane, decahydronaphthalene, benzene, toluene, xylene, (o-, m-, or para-)diethylbenzene, 1,3,5-trimethylbenzene, naphthalene, mesitylene, and para-trimethylbenzene. Alkane, ortho Alkane, meta Alkane, diphenyl Alkanes, limonene, α-terpenes, β-terpenes, γ-terpenes, camphene, norbornene, pinane, α-pinane, β-pinane, carene, longleafene, rosinane, terpene solvents, etc.

[0208] Examples of the aforementioned esters include: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl octanoate, methyl decanoate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, dimethyl adipate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, etc.

[0209] Alternatively, cyclic esters such as lactones can also be used as the aforementioned esters. Examples of lactones include: β-propiolactone, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptanolactone, γ-octanolactone, γ-nonanolactone, γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, δ-valerolactone, δ-caprolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, ε-caprolactone, etc.

[0210] Examples of the aforementioned ethers include: di-n-propyl ether, ethyl-n-butyl ether, di-n-butyl ether, ethyl-n-pentyl ether, di-n-pentyl ether, ethyl-n-hexyl ether, di-n-hexyl ether, di-n-octyl ether, and ethers with branched hydrocarbon groups such as diisopropyl ether and diisopentyl ether corresponding to these carbon numbers, as well as dimethyl ether, diethyl ether, methylcyclopentyl ether, diphenyl ether, tetrahydrofuran, dioxane, etc.

[0211] Examples of the aforementioned ketones include: acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, cyclohexanone, isophorone, etc.

[0212] Examples of solvents containing halogen elements include: perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene and other perfluorocarbons; 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane; hydrofluorocarbons such as ZEORORAH (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); Novec HFE-7100; Novec... HFE-7200, Novec7300, Novec7600 (all manufactured by 3M) and other hydrofluoroethers, tetrachloromethane and other chlorocarbons, chloroform and other hydrochlorocarbons, dichlorodifluoromethane and other fluorochlorocarbons, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene and other hydrochlorofluorocarbons, perfluoroethers, perfluoropolyethers, etc.

[0213] Examples of sulfoxide solvents mentioned above include dimethyl sulfoxide, etc.

[0214] Examples of carbonate-based solvents include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate.

[0215] Examples of the aforementioned 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 ... 2-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, 4-methyl-2-pentanol, etc.

[0216] Examples of polyol derivatives that do not contain 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 methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and 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, triethylene glycol monoethyl ether 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 diethyl ether acetate 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 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, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dimethyl ether Propylene 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, butanediol dimethyl ether, butanediol monomethyl ether acetate, butanediol diacetate, glycerol triacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, etc.

[0217] Examples of nitrogen-containing solvents include: formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, 1,3-diethyl-2-imidazolinone, 1,3-diisopropyl-2-imidazolinone, diethylamine, triethylamine, pyridine, etc.

[0218] Examples of the aforementioned organosilicon solvents include: hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecylpentasiloxane, etc.

[0219] Examples of the aforementioned 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, 1-tridecanethiol, etc.

[0220] The solvent described above preferably includes an aprotic solvent. The content of the aprotic solvent is, for example, 80% by mass or more, preferably 90% by mass or more, in 100% by mass of the solvent. The aforementioned solvent is an aprotic solvent, that is, the solvent more preferably contains an aprotic solvent in 100% by mass of 100% by mass of the solvent.

[0221] Aprotic solvents include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxides, carbonate solvents, polyol derivatives, nitrogen-containing solvents, and organosilicon solvents. These can be used alone or in combination of two or more.

[0222] Preferably, one or more of the following are selected from the group consisting of derivatives of polyols, hydrocarbons and ethers:

[0223] From the perspective of cost and solubility, derivatives of polyols (specifically, those without an OH group in the molecule) are preferred. Specifically, 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, and ethylene glycol dimethyl ether are preferred. Ethers, 3-methoxy-3-methyl-1-butyl acetate, 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, dipropylene glycol diacetate. Additionally, propylene carbonate, straight-chain or branched hydrocarbon solvents having 6 to 12 carbon atoms are also preferred. Alkane, diphenyl Alkanes, limonene, terpenes, camphene, norbornene, pinane, etc.

[0224] As an example of a surface treatment agent composition comprising a silylating agent and a solvent, the following may also be used: the silylating agent comprises hexamethyldisilazane, heptamethyldisilazane, N-(trimethylsilyl)dimethylamine, bis(dimethylamino)dimethylsilane, bis(trimethylsilyl)trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-trimethylsilylimidazolium, trimethylsilyltriazole, etc. The solvent comprises one or more of the following groups: bis(trimethylsilyl)sulfate, 2,2,5,5-tetramethyl-2,5-disil-1-azacyclopentane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, hexamethyldisiloxane, trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl benzenesulfonate, and trimethylsilyl toluenesulfonate; the solvent comprises a straight-chain hydrocarbon solvent selected from propylene carbonate and having 7 to 10 carbon atoms. It comprises one or more of the following groups: alkyl, pinane, γ-butyrolactone, propylene glycol monomethyl ether acetate and 3-methoxy-3-methyl-1-butyl acetate.

[0225] The surface treatment agent composition may also be water-free or contain water in an amount of less than 2% by mass in 100% by mass of the surface treatment agent composition. Such substantially water-free surface treatment agent compositions can be used.

[0226] The surface treatment agent composition described above may contain other components besides those described above, without hindering the objectives of the present invention. Examples of such other components include oxidants such as hydrogen peroxide and ozone, surfactants, and antioxidants such as BHT.

[0227] The surface treatment agent composition of this embodiment can be obtained by mixing the above-described components. The resulting mixture can also be purified using an adsorbent, filter, or the like as needed. Alternatively, the components can be purified beforehand by distillation or by using an adsorbent, filter, or the like.

[0228] The embodiments of the present invention have been described above, but these are merely examples, and various configurations other than those described can be employed. Furthermore, the present invention is not limited to the above embodiments, and modifications and alterations that achieve the objectives of the present invention are included within its scope.

[0229] Example

[0230] The present invention will be described in detail below with reference to the embodiments, but the present invention is not limited to the description of these embodiments.

[0231] <Preparation of Surface Treatment Agent Composition>

[0232] (Surface treatment agent composition 1)

[0233] N-(trimethylsilyl)dimethylamine (TMSDMA) and propylene glycol monomethyl ether acetate (PGMEA) were mixed at 25°C and stirred for 1 minute to prepare surface treatment agent composition 1 containing 1% by mass of TMSDMA as a silylating agent. Surface treatment agent composition 1 was used within 30 minutes of preparation for the surface treatments described below. Hereinafter, "within 30 minutes of preparation" will be expressed as "immediately after preparation".

[0234] (Surface treatment agent composition 2)

[0235] N-(trimethylsilyl)dimethylamine (TMSDMA) and propylene glycol monomethyl ether acetate (PGMEA) were mixed at 25°C and stirred for 1 minute. Then, trifluoroacetic acid (TFA) was added to react with TMSDMA, thereby preparing surface treatment agent composition 2 containing 0.1% by mass of trimethylsilyl trifluoroacetate (TMSTFA) as compound A and 1% by mass of TMSDMA as a silylating agent. The surface treatment described below uses the freshly prepared surface treatment agent composition 2.

[0236] (Surface treatment agent composition 3)

[0237] Surface treatment agent composition 3 was prepared by the same method as surface treatment agent composition 2, except that TMSDMA was replaced with hexamethyldisilazane (HMDS). The newly prepared surface treatment agent composition 3 was used in the surface treatments described later.

[0238] (Surface treatment agent compositions 4-37)

[0239] Surface treatment agent compositions 4 to 37 were prepared by the same method as those described in Table 1, except for the raw materials listed in Table 1. The freshly prepared surface treatment agent compositions 4 to 37 were used in the surface treatments described later. It should be noted that the abbreviations and compound names in Table 1 are shown in Table 2.

[0240] <Preparation for evaluating the substrate wound around to the back side>

[0241] Prepare a silicon dioxide wafer, wherein the aforementioned silicon dioxide wafer has "a main surface having a smooth thermal oxide film and a sloped region having an inclined surface (upper slope) present at its periphery and an edge surface at the end of the main surface at a 90-degree angle relative to the main surface".

[0242] The prepared silicon dioxide wafer was immersed in a 1% hydrofluoric acid aqueous solution at room temperature for 10 minutes, then in pure water at room temperature for 1 minute, and finally in 2-propanol (IPA) at room temperature for 1 minute. It was then dried to prepare it for evaluation of the substrate wound to the back side.

[0243] Manufacturing of patterned substrates

[0244] First, a silicon substrate is prepared as follows: a convex structure with a plurality of generally cylindrical convex portions having a spacing of 90 nm (the total distance of the width of the convex portion and the adjacent spacing of the convex portions) is formed on the surface, and a smooth region without a pattern is formed on its outer periphery. The aforementioned generally cylindrical convex portions have an aspect ratio of 22 in cross-section and a pattern width of 19 nm.

[0245] The surface of the prepared substrate is dry-cleaned using UV / O3 irradiation. This oxidizes the substrate surface into silicon dioxide. Through these steps, a patterned substrate is prepared.

[0246] The portion with a convex structure will be referred to as the "pattern forming area" below.

[0247] It should be noted that the main surface of the substrate used for evaluation of the back side is made of the same material (silicon dioxide) as the main surface of the substrate with the pattern.

[0248] [Table 1]

[0249]

[0250] [Table 2]

[0251] Abbreviation Chemical name TMSTFA Trimethylsilyl trifluoroacetate TMS-TMG N-(trimethylsilyl)tetramethylguanidine MSTFA N-Methyl-N-trimethylsilyltrifluoroacetamide tBu-TMG N-tert-butyldiphenylguanidine DBTMDS 1,3-Di-n-butyl-1,1,3,3-tetramethyldisilazane DOTMDS 1,3-Di-n-octyl-1,1,3,3-tetramethyldisilazane HMDS 1,1,1,3,3,3-Hexamethyldisilazane TMSDMA N-(trimethylsilyl)dimethylamine TMS-Cl Chlorotrimethylsilane TMSDEA N-(trimethylsilyl)diethylamine TMDS 1,1,3,3-Tetramethyldisilazane TMSIm N-(trimethylsilyl)imidazolium DBU 1,8-Dazabicyclo[5,4,0]-7-undecene Im imidazole N-MeIm N-Methylimidazole DBN 1,5-Dazabicyclo[4,3,0]-5-nonene BSTFA N,O-bis(trifluoromethyl)trifluoroacetamide 2-MeIm 2-Methylimidazole TMS amide N-(trimethylsilyl)trifluoroacetamide PGMEA Propylene glycol monomethyl ether acetate DiAE diisopentyl ether nPA 1-Propanol TPGDME Tripropylene glycol dimethyl ether BDMSTFA Butyl dimethyl silyl trifluoroacetate ODMSTFA Octyl dimethyl silyl trifluoroacetate

[0252] In the table, Me represents methyl (-CH3).

[0253] (Substrate surface treatment)

[0254] [Examples I-1 to I-37, Comparative Example I-1]

[0255] The substrate was placed in a spin coater and rotated at 200 rpm while being discharged at a rate of 200 cc / min in the following order: IPA, the surface treatment agent composition described in Table 1, and IPA again. After discharge stopped, the spin was continued in an attempt to remove the IPA.

[0256] It should be noted that in Comparative Example I-1, the above-mentioned surface treatment agent composition was not discharged, but the same treatment as in Examples I-1 to I-37 was performed.

[0257] [Examples W-1 to W-37, Comparative Example 2]

[0258] The substrate was placed in a spin coater and rotated at 200 rpm. The substrate was discharged in the following order: IPA, the surface treatment agent composition described in Table 1, and water, at a rate of 200 cc / min. After discharge stopped, the substrate was continued to rotate in an attempt to remove the water.

[0259] It should be noted that in Comparative Example W-1, the above-mentioned surface treatment agent composition was not discharged, but the same treatment as in Examples W-1 to W-37 was performed.

[0260] <Evaluation of IPA back-side, water back-side return, IPA back angle, water back angle, IPA contact angle, and water contact angle>

[0261] The substrate obtained in the above-mentioned "Surface Treatment of Substrate" for evaluating the back side was taken out of the spin coater, and the distance from the edge surface of the substrate to the back side was measured. The measurement was performed at 8 equally spaced points, and the average value was calculated. The average values ​​of the distance to the back side are shown in Tables 3 and 4.

[0262] Furthermore, after the substrate was dried, it was mounted to a contact angle meter at room temperature (25 degrees Celsius). Approximately 3 μL of IPA was added while the meter was mounted on a horizontal platform. The contact angle of the IPA droplet after it dried naturally and the droplet size decreased (contact angle (°) after 60 seconds of IPA addition) was measured as the IPA back angle. The IPA back angles are shown in Tables 3 and 4.

[0263] In addition, after drying the substrate, a contact angle meter was mounted at room temperature (25°C). 30 μL of pure water was added dropwise while the meter was mounted on a horizontal platform. The pure water was then aspirated at a rate of 6 μL / second to reduce the droplet size. The contact angle of the droplet was continuously measured during this process. The contact angle at which the droplet size decreased without a change in contact angle was taken as the water retreat angle. The water retreat angles are shown in Tables 3 and 4.

[0264] In addition, using a substrate for measuring the IPA backlash angle, the dried substrate was mounted on a contact angle meter. Approximately 1 μL of IPA was added while the substrate was mounted on a horizontal platform. The state of the droplet was observed after 5 seconds, and the contact angle (°) at this time was measured as the IPA contact angle. The IPA contact angles are shown in Tables 3 and 4.

[0265] In addition, using a substrate for measuring the water retraction angle, the dried substrate was mounted on a contact angle meter. Approximately 1 μL of pure water was added while the substrate was mounted on a water platform. The state of the droplet was observed after 5 seconds, and the contact angle (°) at this time was measured as the water contact angle. The water contact angles are shown in Tables 3 and 4.

[0266] <Evaluation of Pattern Collapse Rate>

[0267] In the "surface treatment" of the substrate with the above-described pattern, the substrate is dried while N2 is being discharged after the final IPA is discharged. In the patterned area of ​​the substrate, 500 to 600 protrusions are observed at a magnification of SU8010 (Hitachi High-Tech Corporation) to count the number of collapsed protrusions. The proportion of collapsed protrusions to all protrusions is shown as the pattern collapse rate (%) in Tables 3 and 4.

[0268] [Table 3]

[0269]

[0270] [Table 4]

[0271]

[0272] As shown in Tables 3 and 4, in Examples I-1 to I-37 and Examples W-1 to W-37 using surface treatment agent compositions 1 to 37, an IPA back angle and a water back angle of a specified value or higher were observed. Furthermore, as shown in Tables 3 and 4, the backflow of the rinsing solution was further reduced compared to Comparative Examples I-1 and W-1, which were not treated with the surface treatment agent compositions.

[0273] Furthermore, as shown in Tables 3 and 4, in Examples I-1 to I-37 and Examples W-1 to W-37 using surface treatment agent compositions 1 to 37, an IPA contact angle and a water contact angle of a specified value or higher were observed. As shown in Tables 3 and 4, compared with Comparative Example I-1 and Comparative Example W-1, a good pattern collapse suppression effect was observed.

[0274] 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 contents of which are incorporated herein by reference.

[0275] Explanation of reference numerals in the attached figures

[0276] 10…Substrate

[0277] 12…Main Surface

[0278] 14…Gap

[0279] 16…back

[0280] 20…Concave-convex structure

[0281] 22…convex part

[0282] 24…concave

[0283] 30… Pattern forming area

[0284] 32…areas where the pattern has not yet formed

[0285] 50…bevel area

[0286] 51…apex

[0287] 52…upper slope

[0288] 53…front shoulder

[0289] 54…Edge Face

[0290] 55…lower slope

[0291] 60… Surface treatment agent composition

[0292] 70… Surface treatment agent layer

Claims

1. A processing method for processing the main surface of a semiconductor substrate having a patterned region and a sloped region with an inclined surface formed around the periphery of the patterned region, wherein the pattern has a raised / lowered structure with a pattern size of 30 nm or less, the method comprising the following steps: A surface treatment process involves rotating a surface treatment agent composition to contact the patterned area and the beveled area of ​​the main surface of the semiconductor substrate; the surface treatment agent composition is a liquid containing a silylating agent and a solvent; and Following the surface treatment process, the main surface of the semiconductor substrate is brought into contact with a rinsing solution, and the rinsing solution is then removed by rotating the substrate. The surface treatment agent composition The IPA backlash angle determined by the following steps is 3° or more at room temperature (25°C), and / or The water receding angle calculated using the following steps is greater than 40° at a room temperature of 25 degrees Celsius. step The surface treatment agent composition is brought into contact with the surface of a smooth silicon dioxide substrate to perform surface treatment. When the substrate is placed on a level surface, the surface of the surface-treated silicon dioxide substrate is as follows: 3 μL of 2-propanol was added dropwise at room temperature (25°C), and the contact angle was measured after 60 seconds. This value was taken as the IPA recoil angle. 30 μL of pure water was added dropwise at room temperature (25 degrees Celsius), and then pure water was aspirated at a rate of 6 μL / second. The contact angle during the process of droplet size reduction was measured and this value was taken as the water receding angle.

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

3. The processing method according to claim 1 or 2, wherein, The uneven structure comprises one or more of the following: selected from Si, Ti, Ge, W and Ru, and oxides, nitrides, oxynitrides, carbonitrides and carbon oxides containing one or more of Si, Ti, Ge, W and Ru.

4. The processing method according to claim 3, wherein, The solvent includes aprotic solvents.

5. The processing method according to claim 4, wherein, The solvent contains the aprotic solvent in a 100% by mass fraction of the solvent.

6. The processing method according to claim 4 or 5, wherein, The aprotic solvent comprises one or more of the following: hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxides, carbonate solvents, polyol derivatives without an OH group, nitrogen-containing solvents, and organosilicon solvents.

7. The processing method according to claim 4 or 5, wherein, The solvent contains carbonate solvents or lactones.

8. The processing method according to claim 4 or 5, wherein, The solvent contains propylene carbonate or γ-butyrolactone.

9. The processing method according to claim 4 or 5, wherein, The solvent comprises derivatives of polyols that do not have an OH group.

10. The processing method according to claim 1 or 2, wherein, The silylating agent comprises a silicide 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 Each of the following is an organic group consisting of a hydrocarbon group with 1 to 18 carbon atoms, which contains some or all of the hydrogen atoms and is optionally replaced by fluorine. Each of the following is an organic group consisting of a monovalent functional group bonded to the Si element, which is nitrogen, oxygen, carbon, or halogen. a is an integer from 1 to 3, b is an integer from 0 to 2, and the sum of a and b is 1 to 3.

11. The processing method according to claim 1 or 2, wherein, The silylating agent has a trialkylsilyl group.

12. The processing method according to claim 1 or 2, wherein, The element bonded to Si in the silylating agent is nitrogen.

13. The processing method according to claim 1 or 2, wherein, The content of the silylating agent in the surface treatment agent composition is more than 0.1% by mass and less than 50% by mass in 100% by mass.

14. The processing method according to claim 1 or 2, wherein, The surface treatment agent composition contains a catalyst.

15. The processing method according to claim 14, wherein, The catalyst comprises a mixture selected from trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyl dimethylsilyl trifluoroacetate, butyl dimethylsilyl trifluoromethanesulfonate, hexyl dimethylsilyl trifluoroacetate, octyl dimethylsilyl trifluoroacetate, decyl dimethylsilyl trifluoroacetate, and decyl dimethylsilyl trifluoromethanesulfonate. The following is a combination of one or more of the following: 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 sulfonate ester represented by the following general formula [5], a sulfonamide represented by the following general formulas [6] and [7], a sulfonamide derivative represented by the following general formulas [8] and [9], a sulfonyl methyl compound represented by the following general formula [10], a sulfonyl methyl compound derivative represented by the following general formula [11], an imide, a nitrogen-containing compound, a nitrogen-containing heterocyclic compound, and a silylated heterocyclic compound. R 8 -S(=O)2OH[3] In the above general formula [3], R 8 To select some or all of the hydrogen elements, groups can be chosen from the group consisting of monovalent hydrocarbon groups with 1 to 8 carbon atoms substituted by fluorine elements, and hydroxyl groups. R 8’ -S(=O)2O-Si(H) 3-r (R 9 ) r [4] In the above general formula [4], R 8’ R is a monovalent hydrocarbon group with 1 to 8 carbon atoms, in which some or all of the hydrogen element is optionally replaced by fluorine. 9 Each group is independently selected from at least one monovalent hydrocarbon group consisting of 1 to 18 carbon atoms, chosen from some or all of the hydrogen atoms and optionally substituted with fluorine, where r is an integer from 1 to 3. R 10 -S(=O)2OR 11 [5] In the above general formula [5], R 10 To select groups from the group consisting of a monovalent hydrocarbon group with 1 to 8 carbon atoms that is substituted by fluorine, and a fluorine element, R 11 It 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 Each of these groups can be independently selected from the group consisting of a monovalent hydrocarbon group with 1 to 8 carbon atoms, which is selected from some or all of the hydrogen elements and optionally replaced by fluorine, and a fluorine element. In the above general formula [7], R 13 A divalent hydrocarbon group consisting of 1 to 8 carbon atoms, in which some or all of the hydrogen atoms are optionally replaced by fluorine. ((R 14 -S(=O)2)2N) s Si(H) t (R 15 ) 4-s-t [8] In the above general formula [8], R 14 R is a group independently selected from the group consisting of a monovalent hydrocarbon group with 1 to 8 carbon atoms, which is substituted by fluorine, and a fluorine element, with some or all of the hydrogen elements being chosen. 15 Each of the following groups consists of monovalent hydrocarbon groups with 1 to 18 carbon atoms, each consisting of one or more hydrogen atoms that are optionally replaced by fluorine. The s group is an integer from 1 to 3, and the t group is an integer from 0 to 2. The sum of s and t is less than 3. In the above general formula [9], R 16 R are divalent hydrocarbon groups with 1 to 8 carbon atoms, each independently consisting of some or all of the hydrogen element, which are optionally replaced by fluorine. 17 Each of the following groups consists of 1 to 18 monovalent hydrocarbon groups, each consisting of one or all of a portion of a hydrogen atom that is optionally replaced by fluorine; u is an integer from 1 to 3; v is an integer from 0 to 2; and the sum of u and v is less than 3. (R 18 -S(=O)2)3CH[10] In the above general formula [10], R 18 Each of these groups can be independently selected from the group consisting of a monovalent hydrocarbon group with 1 to 8 carbon atoms, which is selected from some or all of the hydrogen elements and optionally replaced by fluorine, and a fluorine element. ((R 19 -S(=O)2)3C) w Yes(H) x (R 20 ) 4-w-x [11] In the above general formula [11], R 19 R is a group independently selected from the group consisting of a monovalent hydrocarbon group with 1 to 8 carbon atoms, which is substituted by fluorine, and a fluorine element, with some or all of the hydrogen elements being chosen. 20 Each of the following groups consists of 1 to 18 monovalent hydrocarbon groups, each consisting of one or all of the hydrogen elements, which are optionally replaced by fluorine. w is an integer from 1 to 3, x is an integer from 0 to 2, and the sum of w and x is less than 3.

16. The processing method according to claim 14, wherein, The content of the catalyst in the surface treatment agent composition is more than 0.005% by mass and less than 20% by mass in 100% by mass.

17. The processing method according to claim 1 or 2, wherein, The surface treatment agent composition is water-free or contains water in an amount of less than 2% by mass in 100% by mass of the surface treatment agent composition.

18. The processing method according to claim 1 or 2, wherein, The IPA back angle is greater than 5° at room temperature of 25 degrees Celsius, and / or The water receding angle is greater than 50° at room temperature of 25 degrees Celsius.

19. The processing method according to claim 1 or 2, wherein, The IPA contact angle measured by the following steps is greater than 2° and less than 10° at room temperature (25°C), and / or The water contact angle measured using the following steps is greater than 50° at room temperature (25 degrees Celsius). step The surface treatment agent composition is brought into contact with the surface of a smooth silicon dioxide substrate to perform surface treatment. When the substrate is placed on a level surface, the surface of the surface-treated silicon dioxide substrate is as follows: A drop of 1 μL of 2-propanol was added at room temperature (25°C), and the contact angle was measured after 5 seconds. This value was taken as the IPA contact angle. 1 μL of pure water was added at room temperature (25 degrees Celsius), and the contact angle was measured after 5 seconds. This value was taken as the water contact angle.

20. The processing method according to claim 1 or 2, wherein, Prior to the surface treatment process, there is at least one cleaning process that brings the main surface of the semiconductor substrate into contact with an aqueous cleaning solution.

21. The processing method according to claim 20, wherein, The aqueous cleaning solution comprises one or more of the following: water, alcohol, aqueous ammonium hydroxide solution, aqueous tetramethylammonium solution, aqueous hydrochloric acid solution, aqueous hydrogen peroxide solution, aqueous sulfuric acid solution, and organic solvent.

22. The processing method according to claim 20, wherein, The process includes a first rinsing step, which is performed after the cleaning step and before the surface treatment step, and brings the main surface of the semiconductor substrate into contact with a first rinsing solution.

23. The processing method according to claim 1 or 2, wherein, Following the surface treatment process is a drying process that dries the main surface of the semiconductor substrate.

24. The processing method according to claim 1 or 2, wherein, Following the surface treatment process, a removal process is included to remove the surface treatment agent layer formed on the main surface of the semiconductor substrate by the surface treatment process from the main surface.

25. The processing method according to claim 1, wherein, The IPA back angle is greater than 6° at room temperature of 25 degrees Celsius, and / or The water receding angle is above 60° at a room temperature of 25 degrees Celsius.

26. The processing method according to claim 1, wherein, The IPA back angle is greater than 7° at room temperature of 25 degrees Celsius, and / or The water receding angle is above 70° at a room temperature of 25 degrees Celsius.

27. The processing method according to claim 1, wherein, The IPA back angle is less than 20° at room temperature of 25 degrees Celsius, and / or The water receding angle is below 100° at room temperature (25 degrees Celsius).

28. The processing method according to claim 19, wherein, The IPA contact angle is greater than 3° and less than 10° at room temperature (25°C), and / or The water contact angle is greater than 60° and less than 110° at room temperature (25 degrees Celsius).

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