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 the main surface of a semiconductor substrate having a pattern formation region having a pattern formed thereon and a pattern non-formation region having no pattern formed thereon on the main surface of the substrate, the pattern having a concavo-convex structure with a pattern size of 30 nm or less, the method including a surface treatment step of bringing a surface treatment agent composition containing a silylating agent into contact with the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate, the surface on the pattern non-formation region after the surface treatment step having an IPA contact angle with respect to 2-propanol of 2° or more at room temperature of 25 degrees and / or a water contact angle with respect to pure water of 50° or more at room temperature of 25 degrees.

Description

TECHNICAL FIELD

[0001] The present application relates to a surface treatment method for a semiconductor substrate and a surface treatment agent composition. BACKGROUND

[0002] Various developments have been made so far for a surface treatment method for a semiconductor substrate. As such a technology, for example, the technology described in Patent Literature 1 is known. Patent Literature 1 describes a method of performing surface treatment on the surface of a dummy substrate on which a SiO2 film or a SiN film is formed on a Si substrate different from a Si substrate on which a Si pillar pattern is formed as a whole, and evaluating the water contact angle of the dummy substrate not having a pattern (Example of Patent Literature 1).

[0003] PRIOR ART DOCUMENTS

[0004] PATENT LITERATURE

[0005] Patent Literature 1: WO2018 / 175682 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] However, as a result of the present inventors' studies, it was clarified that there is room for improvement in terms of manufacturing management and manufacturing stability in the surface treatment method for a semiconductor substrate described in the above Patent Literature 1.

[0008] SOLUTION TO PROBLEM

[0009] The present inventors further studied and found the following insights.

[0010] If a semiconductor substrate having a pattern formation region and a pattern non-formation region in which a fine pattern is formed on the main surface is used, it is possible to perform surface treatment on the surface of the pattern formation region and to measure the contact angle with 2-propanol (hereinafter referred to as the IPA contact angle) or the contact angle with pure water (hereinafter referred to as the water contact angle) on the surface of the pattern non-formation region after the surface treatment, that is, since it becomes possible to perform surface treatment on a pattern and to evaluate the IPA contact angle or the water contact angle on the surface after the surface treatment in the same semiconductor substrate, management of the manufacturing process will become easy compared to the case where other dummy substrates are used.

[0011] Based on such insights, further intensive studies were made, and as a result, it was found that not only by adopting the IPA contact angle or the water contact angle on the surface in the pattern non-formation region as an index, it becomes possible to stably evaluate the pattern collapse rate in the pattern formation region, but also by setting the IPA contact angle or the water contact angle to be within a prescribed range, it is possible to further suppress pattern collapse, and thus the present application was completed.

[0012] According to the present application, a treatment method is provided,

[0013] which is a treatment method for treating a main surface of a semiconductor substrate having a patterned region with a pattern formed thereon and a pattern-unformed region without the pattern on a main surface of a substrate, the pattern having a concavo-convex structure with a pattern size of 30 nm or less, comprising the steps of:

[0014] a surface treatment step of bringing a surface treatment agent composition containing a silylating agent into contact with the patterned region and the pattern-unformed region of the main surface of the semiconductor substrate, wherein

[0015] on the surface of the pattern-unformed region after the surface treatment step

[0016] an IPA contact angle for 2-propanol is 2° or more at room temperature of 25°C, and / or

[0017] a water contact angle for pure water is 50° or more at room temperature of 25°C.

[0018] Further, according to the present application, there is provided a surface treatment agent composition,

[0019] which is used for treating a main surface of a semiconductor substrate having a patterned region with a pattern formed thereon and a pattern-unformed region without the pattern on a main surface of a substrate, the pattern having a concavo-convex structure with a pattern size of 30 nm or less,

[0020] the surface treatment agent composition contains a silylating agent,

[0021] an IPA contact angle calculated from the following steps is 2° or more, and / or

[0022] a water contact angle calculated from the following steps is 50° or more.

[0023] (Procedure)

[0024] the surface treatment agent composition is brought into contact with the patterned region and the pattern-unformed region of the main surface of the semiconductor substrate.

[0025] after the surface treatment agent composition is brought into contact, on the surface of the pattern-unformed region,

[0026] a contact angle for 2-propanol is measured at room temperature of 25°C, and the value is taken as an IPA contact angle (°),

[0027] a contact angle for pure water is measured at room temperature of 25°C, and the value is taken as a water contact angle (°).

[0028] Effects of the Invention

[0029] According to the present application, a surface treatment method of a semiconductor substrate excellent in manufacturing manageability and manufacturing stability and a surface treatment agent composition used therefor are provided. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 is a schematic plan view showing the structure of a semiconductor substrate.

[0031] Figure 2 is a schematic cross-sectional view showing the structure of a semiconductor substrate.

[0032] Figure 3 is a schematic process cross-sectional view showing a manufacturing process of a semiconductor substrate. DETAILED DESCRIPTION

[0033] Embodiments of the present application will be described below with reference to the drawings. Note that, in all the drawings, the same symbols are used for the same components, and redundant explanation is not given. In addition, the drawings are schematic views, and the actual dimensional ratios are not consistent with those of the drawings.

[0034] The surface treatment method of the semiconductor substrate of the present embodiment is a treatment method of treating the main surface of a semiconductor substrate having a pattern formation region in which a pattern is formed and a pattern non-formation region in which no pattern is formed on the main surface of the substrate, the pattern having a concavo-convex structure with a pattern size of 30 nm or less.

[0035] The treatment method includes a surface treatment step of bringing a surface treatment agent composition containing a silylating agent into contact with the pattern formation region and the pattern non-formation region of the main surface of the semiconductor substrate, the water contact angle on the surface of the pattern non-formation region after the surface treatment step being 50° or more at room temperature of 25 degrees Celsius and / or the IPA contact angle of 2-propanol being 2° or more at room temperature of 25 degrees Celsius.

[0036] In the above Patent Document 1, the surface treatment method disclosed by the examples and the like is a method in which a smooth dummy substrate surface is surface-treated with a surface treatment composition and the water contact angle is evaluated, and a patterned substrate surface is surface-treated with a surface treatment composition and the pattern collapse rate is evaluated. In order to confirm whether or not a prescribed water repellent property is exerted, the present inventors and the like found that it is necessary to separately evaluate the water contact angle using a smooth dummy substrate, and a more efficient production method (simplification of process management) is desired.

[0037] According to the present inventors' insight, the processing method of the present embodiment is a more efficient production method in which a semiconductor substrate having a pattern-unformed region with a smooth surface in which no pattern is formed on a directional plane, a periphery of a notch, an outer peripheral portion of a wafer, or the like is taken as a processing target, the contact angle is evaluated in the pattern-unformed region of the substrate, and the collapse rate is evaluated in a pattern-formed region in which a pattern is formed. That is, compared with the conventional cumbersome production method in which a dummy smooth substrate is used to separately evaluate the water contact angle, the production method of the present disclosure can use the same substrate as the semiconductor substrate taken as a surface processing target to take a part of the surface after surface processing (the surface of the pattern-unformed region after drying after surface processing and rinsing) as an evaluation target without evaluating the dummy smooth substrate, and thus can be said to be a more efficient (simplified process management) production method.

[0038] Note that the area of the pattern-unformed region per 1 measurement point of the contact angle in the semiconductor substrate taken as a processing target is preferably 200 mm 2 More preferably, 300 mm 2 Further preferably, 350 mm 2 In particular, 400 mm 2 or more.

[0039] In addition, the rinsing solution after surface processing (the "second rinsing solution" described later) sometimes uses isopropyl alcohol (IPA), water, and the present inventors have found that, in such an embodiment, the capillary phenomenon acting on the pattern at the time of drying of IPA and water further decreases, and even further suppresses the collapse of the pattern, and thus it is desirable that the IPA contact angle of the surface treatment agent layer formed by surface processing be further large and / or the water contact angle of the surface treatment agent layer formed by surface processing be further large.

[0040] In addition, in some embodiments, water and IPA are sometimes used as the rinsing solution after surface processing (the "second rinsing solution" described later) to be rinsed in this order (for example, "surface processing → water rinsing → IPA rinsing", "surface processing → IPA rinsing → water rinsing", and the like), and the present inventors have found that, in such an embodiment, it is desirable that the IPA contact angle and the water contact angle be further large.

[0041] Processing method of another embodiment of the present invention

[0042] is a processing method of processing a main surface of a semiconductor substrate having a pattern-formed region in which a pattern is formed and a pattern-unformed region in which the aforementioned pattern is not formed on the main surface of the substrate, the aforementioned pattern having a concavo-convex structure with a pattern size of 30 nm or less, and the processing method includes the following steps:

[0043] a surface treatment step of bringing a surface treatment agent composition containing a silylating agent into contact with the pattern formation region and the pattern non-formation region of the aforementioned main surface of the aforementioned semiconductor substrate, and

[0044] an evaluation step of determining whether or not the IPA contact angle with 2-propanol on the surface of the pattern non-formation region after the aforementioned surface treatment step is 2° or more, and / or

[0045] the water contact angle with pure water is 50° or more.

[0046] In the evaluation step, the modification state on the surface of the semiconductor substrate can be evaluated using the IPA contact angle or the water contact angle as an index, and in the case where one or both of them are determined to be a prescribed value or more, the subsequent substrate processing step can be performed. As the subsequent step, for example, a second rinsing step, a drying step, a removal step, a publicly known substrate surface treatment which has not been performed, and the like can be cited. In addition, in the case where it is not a prescribed value or more, the evaluation step can be performed after the surface treatment step is performed again.

[0047] Therefore, since the progress of the step can be determined in the production line without performing the contact angle evaluation using a dummy substrate as an additional step, the manufacturing management becomes easy. In addition, since the collapse of the pattern in the pattern formation region after the step is performed can be suppressed, the manufacturing stability can be improved.

[0048] In the present application, the IPA contact angle on the surface of the pattern non-formation region of the main surface after the surface treatment is 2° or more, preferably 3° or more, at room temperature of 25 degrees; and / or

[0049] the water contact angle is 50° or more, preferably 55° or more, more preferably 60° or more, at room temperature of 25 degrees.

[0050] Thereby, the collapse rate of the pattern in the pattern formation region can be reduced.

[0051] On the other hand, the aforementioned IPA contact angle can be set to, for example, 10° or less, and the aforementioned water contact angle can be set to, for example, 110° or less, or can be set to, for example, 99° or less.

[0052] The IPA contact angle and the water contact angle can be measured on the surface of the surface treatment agent layer formed on the surface of the pattern non-formation region by the surface treatment step.

[0053] As the timing of measurement after the surface treatment, it is possible to measure after the "post-rinse step performed after the surface treatment step" or after the "subsequent drying step" following the "surface treatment step of contacting the surface of the main surface of the semiconductor substrate with the surface treatment agent composition". It is also possible to use the timing of measurement of the contact angle immediately before "removing the surface treatment agent layer" following "removing the surface treatment agent composition or other liquid from the surface of the pattern-unformed region". At least one of these timings can be used.

[0054] In the present specification, immediately after ···, immediately before ··· means within 24 hours, preferably within 2 hours, and particularly preferably within 30 minutes.

[0055] In addition, according to the surface treatment method of the present application, the standard deviation of the IPA contact angle at the prescribed 10 places in the pattern-unformed region can be, for example, 2° or less. In addition, the difference between the maximum value and the minimum value of the IPA contact angle can be, for example, 5° or less.

[0056] Similarly, the standard deviation of the water contact angle at the prescribed 10 places in the pattern-unformed region can be, for example, 2° or less. In addition, the difference between the maximum value and the minimum value of the water contact angle can be, for example, 5° or less.

[0057] It is known that in the manufacturing process of semiconductor elements in which a semiconductor substrate (wafer) is formed, foreign matter (particles) such as metal particles and inorganic particles adhere to the bevel and the like located at the end portion of the semiconductor wafer.

[0058] By forming a surface treatment agent layer having the above-described IPA contact angle and / or water contact angle on the main surface of the pattern-unformed region and / or the bevel region, it is also possible to reduce the reattachment of foreign matter to the bevel region, the pattern-unformed region.

[0059] In addition, the surface treatment agent composition of the present embodiment is for treating the main surface of a semiconductor substrate having a pattern-formed region in which a pattern is formed and a pattern-unformed region in which no pattern is formed on the main surface of the substrate, and the aforementioned pattern has a concave-convex structure with a pattern size of 30 nm or less.

[0060] Such a surface treatment agent composition contains a silylating agent and is configured so as to have an IPA contact angle of 2° or more and / or a water contact angle of 50° or more, which are calculated by the following steps.

[0061] The IPA contact angle and the water contact angle are calculated by the following steps.

[0062] The surface treatment agent composition is brought into contact with the pattern-formed region and the pattern-unformed region of the main surface of the semiconductor substrate.

[0063] after the surface treatment agent composition is brought into contact, for the surface of the pattern-unformed region,

[0064] The contact angle using 2-propanol is measured at room temperature of 25 degrees, and this value is taken as the IPA contact angle (°).

[0065] The contact angle using pure water is measured at room temperature of 25 degrees, and this value is taken as the water contact angle (°).

[0066] The IPA contact angle or the water contact angle is the value of the contact angle after 1 μL of a droplet of 2-propanol or pure water is added at room temperature of 25 degrees to the surface of the pattern-unformed region of the substrate on which the semiconductor substrate is placed on a water platform, specifically, to the surface of the surface treatment agent layer formed on the surface of the pattern-unformed region.

[0067] Note that the above contact angle measurement procedure is generally used to evaluate the characteristics of the surface treatment agent composition.

[0068] In the evaluation process of the above treatment method, any one of the measurement temperature of 23 degrees ± 5 degrees, any one of the droplet amount of 0.1 μL to 5 μL, and any one of the measurement timing within 0.1 seconds to 30 seconds after the addition can be selected, and the above contact angle measurement procedure using the selected one as the measurement condition is also acceptable.

[0069] In the present embodiment, for example, by appropriately selecting the kind or the mixing amount of each component included in the surface treatment agent composition, the preparation method of the surface treatment agent composition, and the like, the above IPA contact angle and / or the water contact angle can be controlled. For example, appropriate selection of the kind of silylating agent, other components, and rapid use after mixing the components can be cited as a requirement for setting the above IPA contact angle and / or the water contact angle to a desired numerical range.

[0070] The surface treatment method using the surface treatment agent composition of the present embodiment can realize a semiconductor substrate manufacturing method that is excellent in manufacturing manageability and manufacturing stability.

[0071] (Semiconductor substrate manufacturing method)

[0072] The semiconductor substrate manufacturing method of the present embodiment will be described in detail below.

[0073] As an example of the semiconductor substrate manufacturing method, a method in which a main surface of a semiconductor substrate is subjected to pattern formation, a pre-rinse (first rinse) process, a surface treatment process using a surface treatment agent composition, a post-rinse (second rinse) process, a drying process, removal of a surface treatment agent layer, and the like can be cited.

[0074] The following will be described using Figures 1-3The processes are described.

[0075] Figure 1 is a plan view as viewed in a direction perpendicular to the main surface 12 of the substrate 10 (semiconductor substrate). Figure 2 is a schematic view of a cross-sectional view in a prescribed direction of the substrate 10. Figure 3 (a) to Figure 3 (c) is a schematic view of a process cross-sectional view in a manufacturing process of a semiconductor substrate.

[0076] First, a substrate 10 having a pattern (recess-and-protrusion structure 20) formed on a main surface 12 is prepared.

[0077] In the above preparation process of the substrate 10, the following method, which is an example of a method of forming the recess-and-protrusion structure 20 on the surface of the substrate 10, can also be used.

[0078] First, after the resist is applied to the wafer surface, the resist is exposed through a resist mask, and the exposed resist or the unexposed resist is removed, thereby producing a resist layer having a desired recess-and-protrusion pattern. Alternatively, the resist layer having the recess-and-protrusion pattern can be obtained by pressing a mold having a pattern to the resist. Next, the wafer is etched. At this time, the surface of the substrate corresponding to the recessed portion of the resist pattern is selectively etched. Finally, if the resist layer is peeled off, a wafer (substrate 10) having the recess-and-protrusion structure 20 on the surface can be obtained.

[0079] The wafer having the recess-and-protrusion structure 20 and the material of the recess-and-protrusion structure 20 are not particularly limited.

[0080] As the material of the wafer, various wafers such as a silicon wafer, a silicon carbide wafer, a wafer composed of a plurality of components including a silicon element, a sapphire wafer, and various compound semiconductor wafers can be used.

[0081] As the material of the recess-and-protrusion structure 20, one or two or more selected from the group consisting of Si, Ti, Ge, W, and Ru, and oxides, nitrides, oxynitrides, carbonitrides, and oxycarbides containing one or more of Si, Ti, Ge, W, and Ru can be included. For example, as the material of the recess-and-protrusion structure 20, a silicon-based material such as silicon oxide, silicon nitride, polysilicon, monocrystalline silicon, silicon germanium, a metal-based material such as titanium nitride, tungsten, ruthenium, tantalum nitride, and tin, and a material in which each of these materials is combined, a resist (photoresist) material, and the like can be used.

[0082] Figure 1 The substrate 10 of the recess-and-protrusion structure 20 has a pattern formation region 30 in which a pattern (recess-and-protrusion structure 20) is formed and a pattern non-formation region 32 in which no pattern is formed on the main surface 12.

[0083] Figure 1The substrate 10 can also have a notch portion 14 formed in a part of the peripheral portion. The notch portion 14 can also have a cutout or a V-shaped cutout called a notch that indicates a straight line of the direction of a crystal axis, formed for the purpose of determining the position in an exposure device or the like, called an orientation flat.

[0084] The pattern formation region 30 is a region in which one or more than one concavo-convex structure 20 is formed when viewed in a direction perpendicular to the main surface 12, that is, in plan view. The pattern formation region 30 can also include an element formation region in which one or more than one semiconductor element is formed.

[0085] For the concavo-convex structure 20, for example, a three-dimensional structure having "one or more than one structure body arranged in a direction perpendicular to the main surface 12" and / or "one or more than one structure body arranged in a horizontal direction orthogonal to the perpendicular direction" can be used. As an example of such a three-dimensional structure, at least a part of a logic device or a memory, such as a FinFET, a nanowire FET, a nanosheet FET, or another multi-gate type FET, a three-dimensional memory cell, or the like can be used.

[0086] The pattern non-formation region 32 is a region formed in at least a part of or the entire periphery of the pattern formation region 30 in plan view. The pattern non-formation region 32 can be formed continuously with each other, or can be divided into a plurality of regions.

[0087] At least a part of the pattern non-formation region 32 has a smooth flat region in which the concavo-convex structure 20 is not formed.

[0088] One or more than one cutting region for cutting can be formed in the pattern formation region 30 and / or between the pattern formation region 30 and the pattern non-formation region 32.

[0089] Figure 2 is a cross-sectional view showing an example of the concavo-convex structure 20.

[0090] In the present embodiment, the pattern size of the concavo-convex 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.

[0091] At least one or more of the pattern sizes of the width and the height in the cross-sectional structure (in the substrate thickness direction) of the pattern of the concavo-convex structure 20, or at least one or more of the pattern sizes of the width (length in the X-axis direction), the height (length in the Y-axis direction), and the depth (length in the Z-axis direction) in the three-dimensional structure (three-dimensional coordinates of XYZ) of the pattern of the concavo-convex structure 20, for example, can be 30 nm or less, 20 nm or less, or 10 nm or less. It can also be the interval between the patterns. The surface treatment agent composition of the present embodiment can also be applied in the case where the substrate 10 having such a fine concavo-convex structure 20 is used.

[0092] Such a surface treatment agent composition is suitable as one for surface-treating a substrate 10 having a concavo-convex structure 20 whose pattern size is, for example, 30 nm or less, preferably 20 nm or less.

[0093] The aspect ratio of the convex portion 22 can be specifically 3 or more, 5 or more, or 10 or more. The pattern collapse can be suppressed even in the concavo-convex structure 20 having a fragile structure of the convex portion 22.

[0094] On the other hand, the aspect ratio of the convex portion 22 is not particularly limited and can be 100 or less.

[0095] The aspect ratio of the convex portion 22 is indicated by the value obtained by dividing the height of the convex portion 22 by the width of the convex portion 22.

[0096] The substrate 10 can also have a bevel region 50 formed at least in part of the end portion of the substrate 10, as shown in FIGS. 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, and 50. Figure 1 2 The substrate 10 can also have a bevel region 50 formed at least in part of the end portion of the substrate 10, as shown in FIGS. 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, and 50.

[0097] Next, the main surface 12 of the substrate 10 can also be brought into contact with an aqueous cleaning solution as needed (cleaning step).

[0098] As the aqueous cleaning solution, for example, water, alcohol, an aqueous ammonium hydroxide solution, an aqueous tetramethylammonium solution, an aqueous hydrochloric acid solution, an aqueous hydrogen peroxide solution, an aqueous sulfuric acid solution, and an organic solvent, etc. can be exemplified. These can be used alone or in combination of two or more.

[0099] The cleaning step can be performed once or two or more times before the surface treatment step or before the first rinsing step. Other steps can also be included between the plurality of cleaning steps or between the cleaning step and the surface treatment step.

[0100] ​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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] The method of supplying the surface treatment agent composition 60 can use known means, but for example, a single wafer type represented by a spin method (spin coating method) is preferable, and the composition is supplied to the vicinity of the rotation center while rotating a wafer one by one almost horizontally to replace the cleaning liquid or the like held in the concave-convex pattern of the wafer, thereby filling the composition. An intermittent method or the like can also be used, and the intermittent method is to immerse a plurality of wafers in a composition tank to replace the cleaning liquid or the like held in the concave-convex pattern of the wafer, thereby filling the composition.

[0108] Next, as shown in (b), the 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. Figure 3

[0109] The surface treatment agent composition 60 on the main surface 12 can also be subjected to a heating treatment, a reduced pressure treatment, a drying treatment, or the like as needed to facilitate the formation of the surface treatment agent layer 70.

[0110] The surface treatment agent layer 70 is formed on at least the pattern formation region 30 and the pattern non-formation region 32 of the main surface 12 of the substrate 10. The surface treatment agent layer 70 can be formed on the inclined surface region 50 of the main surface 12, or can be formed on the entire main surface 12.

[0111] Next, the main surface 12 on which the surface treatment agent layer 70 is formed can also be brought into contact with a second rinsing liquid as needed (second rinsing step).

[0112] As the second rinsing liquid, those exemplified in the first rinsing liquid can be used.

[0113] In addition, a plurality of second rinsing liquids can also be used. Specifically, rinsing can be performed in the order of water → an organic solvent such as isopropyl alcohol, or in the order of an organic solvent such as isopropyl alcohol → water.

[0114] The second rinsing step can be performed once or two or more times after the surface treatment step. Other steps can also be included between the plurality of second rinsing steps, or between the second rinsing step and the surface treatment step.

[0115] Next, a drying step of drying the main surface 12 of the substrate 10 can also be performed as needed.

[0116] Through the drying step, liquid present on the main surface 12 of the substrate 10 can be removed.

[0117] As the drying means, known means such as a spin drying method, an IPA (2-propanol) vapor drying, a Marangoni drying, a heating drying, a hot air drying, a vacuum drying, or the like can be used.

[0118] ​The drying step can also be performed once or two or more times, for example, after the surface treatment step, after the second rinsing step. Note that the drying step and the second rinsing step can also be alternately repeated.

[0119] Next, as shown in Figure 3 (c), the surface treatment agent layer 70 on the main surface 12 of the substrate 10 can also be removed (removal step).

[0120] As the removal means, heating, UV irradiation, ozone exposure, plasma irradiation, corona discharge, and the like can be given. In addition, treatment using a concentrated fluid such as a supercritical fluid (may also contain an acid, a base, an oxidizing agent), vapor treatment can also be performed. These can be used alone or two or more can be used in combination. These treatments can also be performed under atmospheric pressure or under reduced pressure.

[0121] By the above, a semiconductor substrate (substrate 10) using the surface treatment agent composition of the present embodiment can be obtained.

[0122] As shown in Figure 3 The manufacturing method shown in is one that takes a wafer pattern as the object, but the present application is not limited thereto. With the manufacturing method of the substrate of the present embodiment, by taking a resist pattern as the object, using the surface treatment agent composition of the present application in the cleaning, drying step thereof, collapse of the resist pattern can also be suppressed.

[0123] The above supply step is described in relation to a manufacturing method that is performed after the cleaning step, but is not limited thereto, and can also be performed after various treatments performed on the concave-convex structure 20.

[0124] The manufacturing method of the substrate can also use one or two or more known treatments in addition to the above steps. For example, a surface treatment such as plasma treatment can also be performed after the above removal step.

[0125] Next, the surface treatment agent composition used in the surface treatment of the above semiconductor substrate will be described.

[0126] The surface treatment agent composition of the present embodiment contains a silylating agent.

[0127] The above silylating agent can use a known silylating agent. As the silylating agent, a silicide represented by the following general formula [1], for example, can be used. These can be used alone or two or more can be used in combination.

[0128] R 1 a Si(H) b X 4-a-b [1]

[0129] In the above general formula [1], R1 each independently of the other is an organic group containing a part or all of a hydrogen element optionally substituted with a fluorine element, X each independently of the other is a monovalent organic group whose element bonded to the Si element is nitrogen, oxygen, carbon, or halogen, a is an integer of 1 to 3, b is an integer of 0 to 2, and the sum of a and b is 1 to 3.

[0130] R in the above general formula [1] 1 Not only hydrogen, carbon, nitrogen, oxygen, fluorine elements, but also silicon, sulfur, halogen elements other than fluorine, and the like can be contained.

[0131] In addition, R in the above general formula [1] 1 An unsaturated bond, an aromatic ring, a cyclic structure can also be contained.

[0132] As R in the above general formula [1] 1 , at least one group selected from C e H 2e+1 (e = 1 to 18) and C f F 2f+1 CH2CH2(f = 1 to 8) can be exemplified. Among them, a silane having a trialkylsilyl group can be used.

[0133] Note that, in R in the above general formula [1] 1 In the case where a silicon element is contained, a structure of the general formula [1-1] shown below can also be taken.

[0134] R 1 m X 3-m-n (H) n Si-(CH2) p -Si(H) n X 3-m-n R 1 m [1-1]

[0135] Note that, in the above general formula [1-1], R 1 (wherein the R 1 does not contain a silicon element) and X are the same as those in the above general formula [1], m is an integer of 1 to 2, n is an integer of 0 to 1, the sum of m and n is 1 to 2, p is an integer of 1 to 18, and the methylene chain represented by -(CH2)p- is optionally substituted with a halogen.

[0136] In X in the above general formula [1], the monovalent organic group whose element bonded to the Si element is nitrogen, oxygen, or carbon not only contains hydrogen, carbon, nitrogen, oxygen elements, but also can contain silicon, sulfur, halogen elements, and the like.

[0137] As examples of the monovalent organic group of nitrogen bonded to Si element, for example, isocyanate group, amino group, dialkylamino group, isothiocyanate group, azido group, acetylamino group, -NHC(=O)CF3, -N(CH3)C(=O)CH3, -N(CH3)C(=O)CF3, -N=C(CH3)OSi(CH3)3, -N=C(CF3)OSi(CH3)3, -NHC(=O)-OSi(CH3)3, -NHC(=O)-NH-Si(CH3)3, imidazole ring, triazole ring, tetrazole ring, oxazolidinone ring, morpholine ring, -NH-C(=O)-Si(CH3)3, -N(S(=O)2R 4 )2(wherein R 4 each independently represents a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine element, and fluorine element, and a substituent group having the following general formula [1-2]

[0138]

[0139] (in the above general formula [1-2], R 5 each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine element.), -N=C(NR 62 )2, -N=C(NR 62 )R 6 (wherein R 6 each independently represents a group selected from the group consisting of hydrogen group, -C≡N group, -NO2 group, and a hydrocarbon group in which a part or all of hydrogen elements are optionally substituted with fluorine element, and the above hydrocarbon group can have an oxygen atom and / or a nitrogen atom.), -N(R a1 )(R a2 )(wherein the above R a1 represents a hydrogen atom or a saturated or unsaturated alkyl group, and R a2 represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a saturated or unsaturated heterocycloalkyl group.), -N(R a1 and R a2 may be bonded to each other to form a saturated or unsaturated heterocycloalkyl group having a nitrogen atom.), -N(R a3 )-Si(R a4 )(R a5 )(R a6 )(wherein the above R a3 represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, trimethylsilyl group, or dimethylsilyl group, and the above R a4 , R a5 , and R a6 each independently represents a hydrogen atom or an organic group, and R a4 , R a5and R a6 The total number of carbon atoms contained is 1 or more., -N(R a7 )-C(=O)R a8 (Here, the above R a7 represents a hydrogen atom, a methyl group, a trimethylsilyl group or a dimethylsilyl group, R a8 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group or a trialkylsilyl amino group., etc.

[0140] As the silylating agent in which X in the above general formula [1] is a monovalent organic group of an element bonded to the Si element which is nitrogen, for example, CH3Si(NH2)3, C2H5Si(NH2)3, C3H7Si(NH2)3, C4H9Si(NH2)3, C5H 11 Si(NH2)3, C6H 13 Si(NH2)3, C7H 15 Si(NH2)3, C8H 17 Si(NH2)3, C9H 19 Si(NH2)3, C 10 H 21 Si(NH2)3, C 11 H 23 Si(NH2)3, C 12 H 25 Si(NH2)3, C 13 H 27 Si(NH2)3, C 14 H 29 Si(NH2)3, C 15 H 31 Si(NH2)3, C 16 H 33 Si(NH2)3, C 17 H 35 Si(NH2)3, C 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 19Si(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 37 Si(CH3)(NH2)2, (CH3)3SiNH2, C2H5Si(CH3)2NH2, (C2H5)2Si(CH3)NH2, (C2H5)3SiNH2, C3H7Si(CH3)2NH2, (C3H7)2Si(CH3)NH2, (C3H7)3SiNH2, C4H9Si(CH3)2NH2, (C4H9)3SiNH2, C5H 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 18H 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, C3F7CH2CH2Si(NH2)3, C4F9CH2CH2Si(NH2)3, C5F 11 CH2CH2Si(NH2)3, C6F 13 CH2CH2Si(NH2)3, C7F 15 CH2CH2Si(NH2)3, C8F 17 CH2CH2Si(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 17CH2CH2Si(CH3)2NH2, CF3CH2CH2Si(CH3)(H)NH2, aminodimethylvinylsilane, aminodimethylphenylethylsilane, aminodimethylphenylsilane, aminomethyldiphenylsilane, aminodimethyl-t-butylsilane, and the like, or the amino group (-NH2group) of the aforementioned aminosilanes is replaced with -N=C=O, dialkylamino (-N(CH3)2, -N(C2H5)2, and the like), t-butylamino, allylamino, -N=C=S, -N3, -NHC(=O)CH3, -NHC(=O)CF3, -N(CH3)C(=O)CH3, -N(CH3)C(=O)CF3, -N=C(CH3)OSi(CH3)3, -N=C(CF3)OSi(CH3)3, -NHC(=O)-OSi(CH3)3, -NHC(=O)-NH-Si(CH3)3 (e.g., N,N'-bis(trimethylsilyl)urea, and the like), an imidazole ring (e.g., N-trimethylsilylimidazole, and the like), a triazole ring (e.g., N-trimethylsilyltriazole, and the like), a tetrazole ring, an oxazolidinone ring, a morpholine ring, -NH-C(=O)-Si(CH3)3, -N(S(=O)2R 4 )2(wherein, R 4 each independently of one another is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or the whole of hydrogen elements are optionally substituted with fluorine elements, and a fluorine element. For example, N-(trimethylsilyl)bis(trifluoromethylsulfonyl)imide, and the like.), and a substituent having a structure of the following general formula [1-2]

[0141]

[0142] (in the above general formula [1-2], R 5 each independently of one another is a divalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or the whole of hydrogen elements are optionally substituted with fluorine elements. For example, N-(trimethylsilyl)-N,N-difluoromethane-1,3-di(sulfonyl)imide, and the like.), -N=C(NR 62 )2, -N=C(NR 62 )R 6 (wherein, R 6 each independently of one another is selected from a hydrogen group, a -C≡N group, a -NO2 group, and a hydrocarbon group in which a part or the whole of hydrogen elements are optionally substituted with fluorine elements, and the aforementioned hydrocarbon group can also have an oxygen atom and / or a nitrogen atom. For example, 2-trimethylsilyl-1,1,3,3-tetramethylguanidine, and the like.), -N(R a1 )R a2 (wherein, the aforementioned R a1 represents a hydrogen atom or a saturated or unsaturated alkyl group, and R a2 represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a saturated or unsaturated heterocycloalkyl group.a1 and R a2 may also be bonded to each other to form a saturated or unsaturated heterocyclic alkyl group having a nitrogen atom., -N(R a3 )-Si(R a4 )(R a5 )(R a6 )(wherein the above R a3 represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a trimethylsilyl group or a dimethylsilyl group, and the above R a4 , R a5 and R a6 each independently represents a hydrogen atom or an organic group, and the total number of carbon atoms contained in R a4 , R a5 and R a6 is 1 or more. For example, 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, pentamethylenyldisilazane, pentamethylpropyldisilazane, pentamethylethyldisilazane, pentamethyl-t-butyldisilazane, pentamethylphenyldisilazane, trimethyltriethyldisilazane, etc., -N(R a7 )-C(=O)R a8 (wherein the above R a7 represents a hydrogen atom, a methyl group, a trimethylsilyl group or a dimethylsilyl group, and R a8 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group or a trialkylsilyl amino group. For example, N-trimethylsilylacetamide, N-trimethylsilyl trifluoroacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyl trifluoroacetamide, bis(trimethylsilyl)acetamide, bis(trimethylsilyl) trifluoroacetamide, etc. ) and the like.

[0143] As the silylating agent in which X in the above general formula [1] is a monovalent organic group of an element bonded to the Si element, an element of oxygen, for example, a silylating agent in which the amino group (-NH2 group) of the above amino silane is replaced by -O-C(=A)R a9 (wherein the above A represents O, CHR a10 , CHOR a10 , CR a10 R a10 or NR a11 , R a9 , R a10respectively, independently represent a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a fluorine-containing alkyl group, a chlorine-containing alkyl group, a trialkylsilyl group, a trialkylsiloxy group, an alkoxy group, a phenyl group, a phenylethyl group or an acetyl group, and the above-mentioned R a11 represents a hydrogen atom, an alkyl group or a trialkylsilyl group. For example, trimethylsilyl acetate, dimethylsilyl acetate, monomethylsilyl acetate, trimethylsilyl trifluoroacetate, dimethylsilyl trifluoroacetate, monomethylsilyl trifluoroacetate, trimethylsilyl trichloroacetate, trimethylsilyl propionate, trimethylsilyl butyrate, etc. a12 ) = N(R a13 ) (here, the above-mentioned R a12 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group or a trialkylsilyl amino group, and R a13 represents a hydrogen atom, an alkyl group, a trialkylsilyl group. a14 ) = CH-C(=O)R a15 ) (here, the above-mentioned R a14 and R a15 respectively, independently represent a hydrogen atom or an organic group. For example, trimethylsilyloxy-3-penten-2-one, 2-trimethylsiloxy-pent-2-en-4-one, etc. a16 ) (here, the above-mentioned R a16 represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a fluorine-containing alkyl group. For example, CH3Si(OCH3)3, C2H5Si(OCH3)3, C3H7Si(OCH3)3, C4H9Si(OCH3)3, C5H 11 Si(OCH3)3, C6H 13 Si(OCH3)3, C7H 15 Si(OCH3)3, C8H 17 Si(OCH3)3, C9H 19 Si(OCH3)3, C 10 H 21 Si(OCH3)3, C 11 H 23 Si(OCH3)3, C 12 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 17H 35 Si(OCH3)3, C 18 H 37 Si(OCH3)3, (CH3)2Si(OCH3)2, C2H5Si(CH3)(OCH3)2, (C2H5)2Si(OCH3)2, C3H7Si(CH3)(OCH3)2, (C3H7)2Si(OCH3)2, C4H9Si(CH3)(OCH3)2, (C4H9)2Si(OCH3)2, C5H 11 Si(CH3)(OCH3)2, C6H 13 Si(CH3)(OCH3)2, C7H 15 Si(CH3)(OCH3)2, C8H 17 Si(CH3)(OCH3)2, C9H 19 Si(CH3)(OCH3)2, C 10 H 21 Si(CH3)(OCH3)2, C 11 H 23 Si(CH3)(OCH3)2, C 12 H 25 Si(CH3)(OCH3)2, C 13 H 27 Si(CH3)(OCH3)2, C 14 H 29 Si(CH3)(OCH3)2, C 15 H 31 Si(CH3)(OCH3)2, C 16 H 33 Si(CH3)(OCH3)2, C 17 H 35 Si(CH3)(OCH3)2, C 18 H 37 Si(CH3)(OCH3)2, (CH3)3SiOCH3, C2H5Si(CH3)2OCH3, (C2H5)2Si(CH3)OCH3, (C2H5)3SiOCH3, C3H7Si(CH3)2OCH3, (C3H7)2Si(CH3)OCH3, (C3H7)3SiOCH3, C4H9Si(CH3)2OCH3, (C4H9)3SiOCH3, C5H 11 Si(CH3)2OCH3, C6H 13 Si(CH3)2OCH3, C7H 15 Si(CH3)2OCH3, C8H 17 Si(CH3)2OCH3, C9H19 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<​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​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 17 CH2CH2Si(CH3)2OCH3, CF3CH2CH2Si(CH3)(H)OCH3, and the like, or a compound in which the methyl portion of the methoxy group of the above methoxysilane is replaced by a monovalent hydrocarbon group having 2 to 18 carbons, optionally substituted with fluorine, or the like., -O-S(=O)2-R a17 (wherein the above R a17 represents an alkyl group having 1 to 6 carbons, a perfluoroalkyl group, a phenyl group, a tolyl group, a -O-Si(CH3)3 group. For example, trimethylsilyl sulfonate, trimethylsilyl benzenesulfonate, trimethylsilyl toluenesulfonate, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl perfluorobutanesulfonate, bis(trimethylsilyl) sulfate, and the like), -O-P(-O-Si(CH3)3)2 (for example, tris(trimethylsilyl) phosphite, and the like), and the like.

[0144] In addition, as the monovalent organic group of X in the above general formula [1] in which X is an element bonded to the Si element and is oxygen, there can be mentioned, for example, hexamethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,1-triethyl-3,3-dimethyldisiloxane, 1,1,3,3-tetra-n-octyldimethyldisiloxane, bis(nonafluorohexyl)tetramethyldisiloxane, 1,3-bis(trifluoropropyl)tetramethyldisiloxane, 1,3-di-n-butyltetramethyldisiloxane, 1,3-di-n-octyltetramethyldisiloxane, 1,3-diethy ltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, hexa-n-butyldisiloxane, hexaethyldisiloxane, hexavinyl disiloxane, 1,1,3,3-tetraisopropyl disiloxane, 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-tetraphenyl dimethyldisiloxane, 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-bis(tert-butyl)disiloxane, vinyl-1,1,3,3-tetramethyldisiloxane, 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-heptamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,5,5,5-hexaethyl-3-methyltrisiloxane, furanyltrisiloxane, tetrakis(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)-1,3-dimethyldisiloxane, tetra-n-propyltetramethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, decamethyltetrasiloxane, dodecamethylhexasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexaphenylcyclotrisiloxane, polydimethylsiloxane, polyoctadecylmethylsiloxane, decamethylcyclopentasiloxane, poly(3,3,3-trifluoropropylmethylsiloxane), polydimethylsiloxane terminated with trimethylsiloxy groups, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, and the like siloxane compounds.

[0145] As the silylating agent in which X in the above general formula [1] is a monovalent organic group of carbon bonded to the Si element, for example, there can be mentioned those in which the amino group (-NH2 group) of the above amino silane is replaced with a -C(S(=O)2R 7 )3 (here, R 7 are each independently of one another a group selected from the group consisting of a monovalent hydrocarbon group of carbon number 1 to 8, in which a part or all of the hydrogen elements are optionally substituted with a fluorine element, and a fluorine element. For example, (trimethylsilyl)tris(trifluoromethylsulfonyl)methide, and the like.

[0146] Further, as the silylating agent in which X in the above general formula [1] is a monovalent organic group of halogen bonded to the Si element, for example, there can be mentioned those in which the amino group (-NH2 group) of the above amino silane is replaced with a chloro group, a bromo group, an iodo group (for example, chlorotrimethylsilane, bromotrimethylsilane, and the like).

[0147] As the silylating agent, a cyclic silazane compound can be included.

[0148] As the cyclic silazane compound, there can be mentioned: a cyclic disilazane compound such as 2,2,5,5-tetramethyl-2,5-disilyl-1-azacyclopentane, 2,2,6,6-tetramethyl-2,6-disilyl-1-azacyclohexane, and the like; a cyclic trisilazane compound such as 2,2,4,4,6,6-hexamethylcyclotrisilazane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane, and the like; a cyclic tetrasilazane compound such as 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane, and the like.

[0149] The above surface treatment agent composition can include, in addition to the above silylating agent, one or more kinds of catalysts for the silylating agent selected from the group consisting of the following compound A, an imide compound, a nitrogen-containing compound, a nitrogen-containing heterocyclic compound not containing a silicon atom, and a silylated heterocyclic compound. Here, the catalyst refers to one that promotes the reaction of the above main surface with the silylating agent, and improves the liquid repellency of the surface treatment agent layer formed, and itself or a modified product thereof can also constitute a part of the surface treatment agent layer.

[0150] The concentration of the above-mentioned catalyst can be, for example, 0.005% by mass or more and 20% by mass or less, or 0.05% by mass or more and 15% by mass or less, relative to the above-mentioned surface treatment agent composition 100% by mass.

[0151] As specific examples of the above-mentioned compound A, for example, trimethylsilyl trifluoroacetate, trimethylsilyl triflate, dimethylsilyl trifluoroacetate, dimethylsilyl triflate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl triflate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl triflate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl triflate, decyldimethylsilyl trifluoroacetate, and decyldimethylsilyl triflate can be listed, and one or more selected from among these can be included. These can be used alone or in combination with two or more.

[0152] Note that the above-mentioned compound A also includes a silylating agent, but in the case of use as a catalyst, it refers to use in combination with another silylating agent other than compound A.

[0153] The above-mentioned compound A can also be one obtained by reacting a silicide represented by the following general formula [2] with an acid or a sulfonic acid selected from one or more of the group consisting of trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride.

[0154] The remaining silicide represented by the following general formula [2] that is not consumed in the reaction can be used as the above-mentioned silylating agent together with the compound A obtained in the reaction. The silicide represented by the following general formula [2] can be reacted with the above-mentioned acid or sulfonic acid, for example, at a molar ratio of 0.2 to 100,000 moles, preferably 0.5 to 50,000 moles, and more preferably 1 to 10,000 moles.

[0155] R 2 c(H)dSi-X [2]

[0156] In the above-mentioned general formula [2], as R 2 c(H)dSi-, the following can be listed: (CH3)3Si-, (CH3)2(H)Si-, (C4H9)(CH3)2Si-, (C6H 13 )(CH3)2Si-, (C8H 17 )(CH3)2Si-, (C 10 H 21 )(CH3)2Si-, and the like. X is the same as in the above-mentioned general formula [1].

[0157] Further, the above-mentioned compound A can also be at least one selected from the group consisting of a sulfonic acid represented by the following general formula [3], an acid anhydride of the sulfonic acid, a salt of the sulfonic acid, and a sulfonic acid derivative represented by the following general formula [4].

[0158] R 8 -S(=O)2OH [3]

[0159] [In the above-mentioned general formula [3], R 8 is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, and a hydroxyl group.]

[0160] R 8’ -S(=O)2O-Si(H) 3-r (R 9 ) r [4]

[0161] [In the above-mentioned general formula [4], R 8’ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, R 9 are each independently at least one group selected from a monovalent hydrocarbon group having 1 to 18 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, and r is an integer of 1 to 3.]

[0162] Further, the above-mentioned compound A can also be at least one selected from the group consisting of a sulfonic acid ester represented by the following general formula [5], a sulfonamide represented by the following general formulae [6] and [7], a sulfonamide derivative represented by the following general formulae [8] and [9], a sulfonylmethylate represented by the following general formula

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

[11] .

[0163] R 10 -S(=O)2OR 11 [5]

[0164] [In the above-mentioned general formula [5], R 10 is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, and a fluorine element, and R 11 is a monovalent alkyl group having 1 to 18 carbon atoms.]

[0165] (R 12 -S(=O)2)2NH [6]

[0166] [In the above-mentioned general formula [6], R 12 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, and a fluorine element.]

[0167]

[0168] [In General Formula [7] above, R 13 is a divalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements.

[0169] ((R 14 -S(=O)2)2N) s Si(H) t (R 15 ) 4-s-t [8]

[0170] [In General Formula [8] above, R 14 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, and a fluorine element, R 15 are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, s is an integer of 1 to 3, t is an integer of 0 to 2, and the total of s and t is 3 or less.

[0171]

[0172] [In General Formula [9] above, R 16 are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, R 17 are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, u is an integer of 1 to 3, v is an integer of 0 to 2, and the total of u and v is 3 or less.

[0173] (R 18 -S(=O)2)3CH

[10]

[0174] [In General Formula

[10] above, R 18 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, and a fluorine element.

[0175] ((R 19 -S(=O)2)3C) w Si(H) x (R 20 ) 4-w-x

[11]

[0176] [In General Formula

[11] above, R 19 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, and a fluorine element, R20 each independently of one another is a monovalent hydrocarbon group having a carbon number of 1 to 18, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, w is an integer of 1 to 3, x is an integer of 0 to 2, and the sum of w and x is 3 or less.

[0177] Further, as the imide compound, for example, a compound having a chemical structure in which a carboxylic acid, a phosphoric acid, or the like is imidized can be exemplified.

[0178] Further, as the nitrogen-containing compound, at least one of the compounds represented by the following general formulae

[12] and

[13] can be exemplified.

[0179] R 21 -N=C(NR 22 2)2

[12]

[0180] R 21 -N=C(NR 22 2)R 22

[13]

[0181] [In the above general formulae

[12] ,

[13] , R 21 is selected from a hydrogen group, a -C≡N group, a -NO2 group, an alkylsilyl group, and a hydrocarbon group in which a part or all of hydrogen elements are optionally substituted with fluorine elements, and the hydrocarbon group can have an oxygen atom and / or a nitrogen atom, but in the case of containing a nitrogen atom, a non-cyclic structure is taken. R 22 each independently of one another is selected from a hydrogen group, a -C≡N group, a -NO2 group, and a hydrocarbon group in which a part or all of hydrogen elements are optionally substituted with fluorine elements, and the hydrocarbon group can have an oxygen atom and / or a nitrogen atom, but in the case of containing a nitrogen atom, a non-cyclic structure is taken.

[0182] Further, as the nitrogen-containing compound, for example, guanidine, 1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, 1,3-diphenylguanidine, 1,2,3-triphenylguanidine, N,N'-diphenylformamidine, 2,2,3,3,3-pentafluoropropylformamidine, and the like can be exemplified.

[0183] Further, as the nitrogen-containing heterocyclic compound not containing a silicon atom and the silylated heterocyclic compound, at least one of the compounds represented by the following general formulae

[14] and

[15] can be exemplified.

[0184]

[0185] [In the above general formula

[14] , R 23 and R 24 each independently is a divalent organic group formed of a carbon element and / or a nitrogen element and a hydrogen element, and the sum of the carbon number and the nitrogen number is 1 to 9, and in the case of 2 or more, a carbon element not constituting a ring can be present.

[0186]

[0187] [In the above general formula

[15] , R 25 is an alkyl group having 1 to 6 carbon atoms, of which a part or all of the hydrogen elements are optionally substituted with fluorine elements, a trialkylsilyl group having 1 to 8 carbon atoms of which a part or all of the hydrogen elements are optionally substituted with fluorine elements, an alkenyl group having 2 to 6 carbon atoms of which a part or all of the hydrogen elements are optionally substituted with fluorine elements, an alkoxy group having 1 to 6 carbon atoms of which a part or all of the hydrogen elements are optionally substituted with fluorine elements, an amino group, an alkylamino group having 1 to 6 carbon atoms of which a part or all of the hydrogen elements are optionally substituted with fluorine elements, a dialkylamino group having 1 to 6 carbon atoms of which a part or all of the hydrogen elements are optionally substituted with fluorine elements, an aminoalkyl group having 1 to 6 carbon atoms of which a part or all of the hydrogen elements are optionally substituted with fluorine elements, a nitro group, a cyano group, a phenyl group, a benzyl group, or a halogen group, R 26 , R 27 , and R 28 are each independently an alkyl group having 1 to 6 carbon atoms of which a part or all of the hydrogen elements are optionally substituted with fluorine elements, or a hydrogen group.]

[0188] In addition, the above-mentioned nitrogen-containing heterocyclic compound not containing a silicon atom can also contain a hetero atom other than a nitrogen atom, such as an oxygen atom or a sulfur atom, in the ring, can also be aromatic, and can be a compound in which two or more rings are bonded via a single bond or a multivalent linking group having a valence of two or more. In addition, the compound can also have a substituent.

[0189] As the above-mentioned nitrogen-containing heterocyclic compound not containing a silicon atom, for example, there can be mentioned pyridine, pyridazine, pyrazine, pyrimidine, triazine, tetrazine, pyrrole, pyrazole, imidazole, triazole, tetrazole, oxazole, isoxazole, thiazole, isothiazole, oxadiazole, thiadiazole, quinoline, isoquinoline, cinnoline, phthalazine, quinoxaline, quinazoline, indole, indazole, benzimidazole, benzotriazole, benzoxazole, benzisoxazole, benzothiazole, benzoisothiazole, benzoxadiazole, benzothiadiazole, saccharin, pyrrolidine, piperidine, and the like.

[0190] In addition, the above-mentioned silylated heterocyclic compound can be mentioned, for example, a silylated imidazole compound, a silylated triazole compound. As an example of the silylated heterocyclic compound, there can be mentioned a monomethylsilylimidazole, a dimethylsilylimidazole, a trimethylsilylimidazole, a monomethylsilyltriazole, a dimethylsilyltriazole, a trimethylsilyltriazole, and the like.

[0191] Note that the above-mentioned silylated heterocyclic compound can also be a silylating agent, but in the case where it is used as a catalyst, it means that it is used in combination with another silylating agent other than the silylated heterocyclic compound.

[0192] 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.

[0193] Surface treatment agent compositions may contain solvents.

[0194] 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.

[0195] These can be used individually or in combination of two or more.

[0196] 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.

[0197] 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.

[0198] In addition, cyclic esters such as lactone compounds can also be used as the above-mentioned esters. Examples of the lactone compounds include β-propiolactone, γ-butyrolactone, γ-valerolactone, γ-hexalactone, γ-heptalactone, γ-octalactone, γ-nonalactone, γ-decalactone, γ-undecalactone, γ-dodecalactone, δ-valerolactone, δ-hexalactone, δ-octalactone, δ-nonalactone, δ-decalactone, δ-undecalactone, δ-dodecalactone, ε-hexalactone, and the like.

[0199] Examples of the above-mentioned 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 having branched hydrocarbon groups such as diisopropyl ether, diisopentyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, methyl cyclopentyl ether, diphenyl ether, tetrahydrofuran, dioxane, and the like.

[0200] Examples of the above-mentioned ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, cyclohexanone, isophorone, and the like.

[0201] Examples of the above-mentioned halogen element-containing solvents include perfluoro-octane, perfluoro-nonane, perfluoro-cyclopentane, perfluoro-cyclohexane, hexafluorobenzene, and the like perfluorocarbons, 1,1,1,3,3-pentafluorobutane, octafluoro-cyclopentane, 2,3-dihydrodecafluoropentane, ZEORORAH (manufactured by Zeon Corporation), and the like hydrofluorocarbons, 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, Novec 7300, Novec 7600 (all manufactured by 3M), and the like hydrofluoroethers, tetrachloromethane and the like chlorocarbons, chloroform and the like hydrochlorocarbons, dichlorodifluoromethane and the like 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 the like hydrofluorochlorocarbons, perfluoroethers, perfluoropolyethers, and the like.

[0202] Examples of the above-mentioned sulfoxide-based solvents include dimethyl sulfoxide and the like.

[0203] Examples of the above-mentioned carbonate-based solvents include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, propylene carbonate, and the like.

[0204] As examples of the above-mentioned alcohols, there are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-l-butanol, 3-methyl-l-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-l-pentanol, 3-methyl-l-pentanol, 4-methyl-l-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-l-butanol, 3,3-dimethyl-l-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-l-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, benzyl alcohol, 1-octanol, isooctyl alcohol, 2-ethyl-l-hexanol, 4-methyl-2-pentanol, and the like.

[0205] As examples of the above-mentioned derivatives of polyhydric alcohols which do not have OH groups, there are ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol 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 diacetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol 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 dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, glycerol triacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, and the like.

[0206] As examples of the above-mentioned nitrogen element-containing solvent, there are formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, diethylamine, triethylamine, pyridine, and the like.

[0207] As examples of the above-mentioned silicone solvent, there are hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and the like.

[0208] As examples of the above-mentioned thiol, there are 1-hexanethiol, 2-methyl-l-pentanethiol, 3-methyl-l-pentanethiol, 4-methyl-l-pentanethiol, 2,2-dimethyl-l- butanethiol, 3,3-dimethyl-l-butanethiol, 2-ethyl-l-butanethiol, 1-heptanethiol, benzyl mercaptan, 1-octanethiol, 2-ethyl-l-hexanethiol, 1-nonanethiol, 1-decanethiol, 1-undecanethiol, 1-dodecanethiol, 1-tridecanethiol, and the like.

[0209] The above-mentioned solvent preferably contains an aprotic solvent. The content of the aprotic solvent is, for example, 80% by mass or more, preferably 90% by mass or more, in 100% by mass of the above-mentioned solvent. The aforementioned solvent is an aprotic solvent, that is, the solvent is more preferably an aprotic solvent containing an aprotic solvent at a content of 100% by mass in 100% by mass of the solvent.

[0210] The aprotic solvent is a hydrocarbon, an ester, an ether, a ketone, a halogen element-containing solvent, a sulfoxide, a carbonate solvent, a derivative of a polyhydric alcohol, a nitrogen element-containing solvent, a silicone solvent, or the like. These can be used alone or in combination of two or more.

[0211] Among them, one or two or more selected from the group consisting of a derivative of a polyhydric alcohol, a hydrocarbon, and an ether is preferably used.

[0212] 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.

[0213] 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.

[0214] 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.

[0215] 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.

[0216] The surface treatment agent composition of the present embodiment can be obtained by mixing the above-described components. The resulting mixture can also be refined as needed using a adsorbent, filter, or the like. In addition, each component can be refined in advance by distillation or using an adsorbent, filter, or the like.

[0217] The above has described the embodiments of the present application, but these are examples of the present application, and various configurations other than the above can be employed. In addition, the present application is not limited to the above-described embodiments, and modifications, etc. within the scope of achieving the object of the present application are included in the present application.

[0218] Example

[0219] The present application is explained in detail below with reference to examples, but the present application is not limited in any way by the description of these examples.

[0220] Manufacture of surface treatment agent composition

[0221] (Surface treatment agent composition 1)

[0222] N-(trimethylsilyl)dimethylamine (TMSDMA) and propylene glycol monomethyl ether acetate (PGMEA) were mixed at a liquid temperature of 25°C, and stirred for 1 minute, to prepare a surface treatment agent composition 1 containing 1 mass% of TMSDMA as a silylating agent. The surface treatment agent composition 1 prepared within 30 minutes was used in the surface treatment described later. Hereinafter, “within 30 minutes after preparation” is expressed as “immediately after preparation”.

[0223] (Surface treatment agent composition 2)

[0224] TMSDMA and PGMEA were mixed at a liquid temperature of 25°C, and stirred for 1 minute. Further, trifluoroacetic acid (TFA) was added, and reacted with TMSDMA, to prepare a surface treatment agent composition 2 containing 0.1 mass% of trimethylsilyl trifluoroacetate (TMSTFA) as Compound A, and 1 mass% of TMSDMA as a silylating agent. The surface treatment agent composition 2 prepared immediately was used in the surface treatment described later.

[0225] (Surface treatment agent composition 3)

[0226] A surface treatment agent composition 3 was prepared in the same manner as the surface treatment agent composition 2, except that TMSDMA was replaced with hexamethyldisilazane (HMDS). The surface treatment agent composition 3 prepared immediately was used in the surface treatment described later.

[0227] (Surface treatment agent compositions 4 to 37)

[0228] Surface treatment agent compositions 4 to 37 were prepared in the same manner as the above surface treatment agent compositions 1, 2 or 3, except that the raw materials described in Table 1 were used. The just-prepared surface treatment agent compositions 4 to 37 were used in the following surface treatment. Note that the abbreviations in Table 1 are shown in Table 2 together with the names of the compounds.

[0229] [Manufacture of substrate]

[0230] First, a silicon substrate was prepared in which a convex structure having a plurality of substantially cylindrical convex portions with a pitch (total distance of width of convex portion and interval between adjacent convex portions) of 90 nm was formed on the surface, and a smooth region in which no pattern was formed was present on the outer peripheral portion, and the aspect ratio of the substantially cylindrical convex portions in cross section was 22 and the pattern width was 19 nm.

[0231] Hereinafter, the portion having the convex structure is referred to as "pattern formation region", and the smooth portion in which no pattern is formed is referred to as "pattern non-formation region".

[0232] Note that the IPA contact angle and water contact angle described later were measured in the pattern non-formation region, and the area of the pattern non-formation region per 1 measurement point of the contact angle at this time was about 250 mm 2 .

[0233] [Surface treatment of substrate]

[0234] The surface of the above substrate was subjected to dry cleaning using UV / O3 irradiation. The surfaces of the pattern formation region and the pattern non-formation region of the above substrate were oxidized to become silicon dioxide. Next, the substrate was set in a spin coater, the substrate was rotated at a speed of 200 rpm, and the following were discharged at a speed of 200 cc / minute in the order of 2-propanol (IPA), the surface treatment agent composition described in Table 1, IPA, and finally N2 was discharged to the substrate, and the substrate was dried.

[0235] Note that in Comparative Example 1, the above surface treatment agent composition was not discharged, and the same treatment was carried out except for this.

[0236] [Table 1]

[0237]

[0238] [Table 2]

[0239] Abbreviation Chemical name TMSTFA trimethylsilyl trifluoroacetamide 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)imidazole DBU 1,8-diazabicyclo[5,4,0]-7-undecene Im imidazole N-MeIm N-methylimidazole DBN 1,5-diazabicyclo[4,3,0]-5-nonene BSTFA N,O-bis(trimethylsilyl)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 n-butyl dimethyl silyl trifluoroacetamide ODMSTFA n-octyl dimethyl silyl trifluoroacetamide

[0240] In the table, Me represents methyl group (-CH3).

[0241] [Evaluation]

[0242] (IPA contact angle)

[0243] The surface-treated silicon substrate was mounted to the contact angle meter at room temperature of 25 degrees, and about 1 μL of 2-propanol (IPA) was added to the pattern-unformed region while being mounted on the water platform, and the state of the droplet after 5 seconds was observed, and the contact angle (°) of the IPA at that time was measured as the IPA contact angle. The IPA contact angle is shown in Table 3.

[0244] (water contact angle)

[0245] The surface-treated silicon substrate was mounted to the contact angle meter at room temperature of 25 degrees, and about 1 μL of 2-propanol (IPA) was added to the pattern-unformed region while being mounted on the water platform, and the state of the droplet after 5 seconds was observed, and the contact angle (°) of the IPA at that time was measured as the IPA contact angle. The IPA contact angle is shown in Table 3.

[0246] (pattern collapse rate)

[0247] Further, the same substrate as used in the measurement of the contact angle was used, and the pattern-formed region was observed with an electron microscope (SEM, SU8010 manufactured by Hitachi High-Tech Corporation) at a magnification at which 500 to 600 of the convex portions would enter the field of view, and the number of convex portions in which pattern collapse occurred was counted. The proportion of the convex portions in which collapse occurred with respect to all the convex portions was taken as the pattern collapse rate (%), and is shown in Table 3.

[0248] [Table 3]

[0249]

[0250] The surface treatment method according to the above-described embodiments of the present disclosure is a more effective method than the existing method in which a dummy smooth substrate is used to evaluate separately, since it is confirmed whether or not a prescribed IPA contact angle and / or a prescribed water contact angle can be exhibited.

[0251] In addition, as shown in Table 1, in Examples 1 to 37 in which the surface treatment agent compositions 1 to 37 were used, an IPA contact angle of a prescribed value or more and a water contact angle of a prescribed value or more were exhibited in the pattern-unformed region of the substrate. Furthermore, as shown in Table 1, the portion of the aforementioned substrate corresponding to the convex portions of the pattern-formed region remained even after the cleaning or drying process, and a result exhibiting a reduction in the pattern collapse rate was exhibited in comparison with Comparative Example 1.

[0252] This application claims priority to Japanese Patent Application No. 2020-089194 filed on May 21, 2020, and Japanese Patent Application No. 2020-089201 filed on May 21, 2020, the disclosures of which are incorporated herein by reference in their entirety.

[0253] Reference Signs

[0254] 10 … substrate

[0255] 12 … main surface

[0256] 14 … notch portion

[0257] 16 … back surface

[0258] 20 … concavo-convex structure

[0259] 22 … convex portion

[0260] 24 … concave portion

[0261] 30 … pattern formation region

[0262] 32 … pattern non-formation region

[0263] 50 … bevel region

[0264] 51 … top edge

[0265] 52 … upper bevel

[0266] 53 … front shoulder

[0267] 54 … edge face

[0268] 55 … lower bevel

[0269] 60 … surface treatment agent composition

[0270] 70 … surface treatment agent layer

Claims

1. A treatment method of treating a main surface of a semiconductor substrate having a patterned region with a pattern formed on a substrate main surface and a pattern-unformed region without the pattern formed on the substrate main surface, the pattern having a concavo-convex structure with a pattern size of 30 nm or less, the treatment method comprising: a surface treatment step of bringing a surface treatment agent composition containing a silylating agent into contact with the patterned region and the pattern-unformed region of the main surface of the semiconductor substrate, the surface treatment step forming a surface treatment agent layer on the entire main surface of the semiconductor substrate, and an evaluation step of judging whether or not a contact angle with 2-propanol, which is calculated in the following steps, is 2° or more at room temperature of 25 degrees, and / or whether or not a water contact angle with pure water, which is calculated in the following steps, is 50° or more at room temperature of 25 degrees, the steps being: a step of dropping a 1-μL droplet of 2-propanol or pure water on a surface of the surface treatment agent layer formed on the pattern-unformed region in a state where the semiconductor substrate is left on a water platform, and a step of measuring a contact angle after 5 seconds of leaving, the value of the contact angle being taken as the IPA contact angle or the water contact angle, respectively. The pattern size is a size in at least one width direction on a plane of the main surface, and / or a size in at least one height direction in a direction perpendicular to the main surface.

3. The treatment method according to claim 1 or 2, wherein: the contact angle on the surface of the surface treatment agent layer is 2° or more at room temperature of 25 degrees, and / or the water contact angle is 55° or more at room temperature of 25 degrees. The concavo-convex structure contains one or two or more selected from the group consisting of Si, Ti, Ge, W, and Ru, oxides, nitrides, oxynitrides, carbonitrides, and oxycarbides of one or more of Si, Ti, Ge, W, and Ru. The surface treatment agent composition contains a solvent. The solvent contains an aprotic solvent. The solvent contains the aprotic solvent at a content of 100 mass% in 100 mass% of the solvent.

2. The treatment method of claim 1, wherein, The aprotic solvent contains one or two or more selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen element-containing solvents, sulfoxides, carbonate solvents, derivatives of polyhydric alcohols not having OH groups, nitrogen element-containing solvents, and silicone solvents. The solvent contains a carbonate solvent or a lactone. The solvent contains propylene carbonate or γ-butyrolactone. The solvent contains one or two or more selected from the group consisting of derivatives of polyhydric alcohols not having OH groups, hydrocarbons, and ethers. The silylating agent contains a silicide represented by the following general formula [1], 4. The treatment method according to claim 1 or 2, wherein, The silylating agent has a trialkylsilyl group.

5. The treatment method according to claim 1 or 2, wherein, The element bonded to a Si element of the silylating agent is nitrogen.

6. The treatment method of claim 5, wherein, The content of the silylating agent is 0.1 mass% or more and 50 mass% or less in 100 mass% of the surface treatment agent composition.

7. The treatment method of claim 6, wherein, The surface treatment agent composition contains a catalyst.

8. The treatment method according to claim 6 or 7, wherein, ​ 9. The treatment method according to claim 6 or 7, wherein, ​ 10. The treatment method according to claim 6 or 7, wherein, ​ 11. The treatment method according to claim 6 or 7, wherein, ​ 12. The treatment method according to claim 1 or 2, wherein, ​ R 1 a Si(H) b X 4-a-b [1] In the above general formula [1], R 1 each independently of the others is an organic group which is a hydrocarbon group having 1 to 18 carbon atoms, part or all of the hydrogen atoms of which are optionally replaced by fluorine atoms, X is each independently of the others a monovalent functional group which is bonded to the Si atom and which is a functional group of an element which is nitrogen, oxygen, carbon or halogen, a is an integer of 1 to 3, b is an integer of 0 to 2, and the sum of a and b is 1 to 3.

13. The treatment method of claim 1 or 2, wherein, ​ 14. The treatment method of claim 1 or 2, wherein, ​ 15. The treatment method of claim 1 or 2, wherein, ​ 16. The treatment method of claim 1 or 2, wherein, ​ 17. The treatment method of claim 16, wherein, The catalyst contains one or two or more selected from the group consisting of trimethylsilyl trifluoroacetate, trimethylsilyl triflate, dimethylsilyl trifluoroacetate, dimethylsilyl triflate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl triflate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl triflate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl triflate, decyldimethylsilyl trifluoroacetate, decyldimethylsilyl triflate, a sulfonic acid represented by the following general formula [3], an acid anhydride of the sulfonic acid, a salt of the sulfonic acid, a sulfonic acid derivative represented by the following general formula [4], a sulfonic acid ester represented by the following general formula [5], a sulfoximine represented by the following general formulae [6] and [7], a sulfoximine derivative represented by the following general formulae [8] and [9], a sulfonylmethyl hydrate represented by the following general formula [10], a sulfonylmethyl hydrate derivative represented by the following general formula [11], an imidate, a nitrogen-containing compound, a nitrogen-containing heterocyclic compound, and a silylated heterocyclic compound, R 8 -S(=0)2OH [3] In General Formula [3] above, R 8 is a group selected from the group consisting of a monovalent hydrocarbon group having a carbon number of 1 to 8, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, and a hydroxyl group, R 8’ -S(=O)2O-Si(H) 3-r (R 9 ) r [4] In the above general formula [4], R 8’ is a monovalent hydrocarbon group having 1 to 8 carbons, of which a part or the whole hydrogen elements are optionally substituted with fluorine elements, R 9 are each independently at least one group selected from a monovalent hydrocarbon group having 1 to 18 carbons, of which a part or the whole hydrogen elements are optionally substituted with fluorine elements, and r is an integer of 1 to 3, R 10 -S(=O)2OR 11 [5] In General Formula [5] above, R 10 is a group selected from the group consisting of a monovalent hydrocarbon group having a carbon number of 1 to 8, in which a part or all of hydrogen elements are optionally substituted with fluorine elements, and a fluorine element, R 11 is a monovalent alkyl group having a carbon number of 1 to 18, (R 12 -S(=O)2)2NH [6] In General Formula [6] above, R 12 each independently of one another is a group selected from the group consisting of a monovalent hydrocarbon group having a carbon number of 1 to 8, in which a part or whole of hydrogen elements are optionally substituted with fluorine elements, and a fluorine element. In the above general formula [7], R 13 a divalent hydrocarbon group having a carbon number of 1 to 8, in which a part or whole of hydrogen elements are optionally substituted with fluorine elements, ((R 14 -S(=O)2)2N) s Si(H) t (R 15 ) 4-s-t [8] In the above general formula [8], R 14 each independently is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or the whole of hydrogen elements are optionally substituted with fluorine elements, and a fluorine element, R 15 each independently is a monovalent hydrocarbon group having 1 to 18 carbon atoms, in which a part or the whole of hydrogen elements are optionally substituted with fluorine elements, s is an integer of 1 to 3, t is an integer of 0 to 2, and the total of s and t is 3 or less, In the above general formula [9], R 16 each independently of the others is a divalent hydrocarbon group having 1 to 8 carbon atoms, of which a part or the whole hydrogen atoms are optionally substituted with fluorine atoms, R 17 each independently of the others is a monovalent hydrocarbon group having 1 to 18 carbon atoms, of which a part or the whole hydrogen atoms are optionally substituted with fluorine atoms, u is an integer of 1 to 3, v is an integer of 0 to 2, and the sum of u and v is 3 or less, (R 18 -S(=O)2)3CH [10] In General Formula [10] above, R 18 each independently is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or whole of hydrogen elements are optionally substituted with fluorine elements, and a fluorine element. ((R 19 -S(=O)2)3C) w Si(H) x (R 20 ) 4-w-x [11] In General Formula [11] above, R 19 each independently is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or the whole of hydrogen elements are optionally substituted with fluorine elements, and a fluorine element, R 20 each independently is a monovalent hydrocarbon group having 1 to 18 carbon atoms, in which a part or the whole of hydrogen elements are optionally substituted with fluorine elements, w is an integer of 1 to 3, x is an integer of 0 to 2, and the total of w and x is 3 or less.

18. The treatment method of claim 16, wherein, The content of the catalyst is 0.005 mass% or more and 20 mass% or less in the surface treatment agent composition 100 mass%.

19. The treatment method of claim 1 or 2, wherein, The surface treatment agent composition contains no water, or contains water in an amount of 2 mass% or less in the surface treatment agent composition 100 mass%.

20. The treatment method according to claim 1 or 2, which uses a spin coating method to contact the surface treatment agent composition with the main surface in the surface treatment step.

21. The treatment method of claim 1 or 2, wherein, Before the surface treatment step, at least one or more cleaning steps of contacting the main surface of the semiconductor substrate with an aqueous cleaning solution are included.

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

23. The treatment method of claim 21, wherein, After the cleaning step and before the surface treatment step, a first rinsing step of contacting the main surface of the semiconductor substrate with a first rinsing solution is included.

24. The treatment method of claim 1 or 2, wherein, After the surface treatment step, a second rinsing step of contacting the main surface of the semiconductor substrate with a second rinsing solution is included.

25. The treatment method of claim 1 or 2, wherein, After the surface treatment step, a drying step of drying the main surface of the semiconductor substrate is included.

26. The treatment method of claim 1 or 2, wherein, After the surface treatment step, a removal step of removing a surface treatment agent layer formed on the main surface of the semiconductor substrate by the surface treatment step from the main surface is included.

27. The treatment method of claim 1, wherein, The IPA contact angle is 3° or more at room temperature 25 degrees, and / or The water contact angle is 55° or more at room temperature 25 degrees.

28. The treatment method of claim 1, wherein, The IPA contact angle is 10° or less at room temperature 25 degrees, and / or The water contact angle is 110° or less at room temperature 25 degrees.

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