WO2021235476A1 - 半導体基板の表面処理方法、及び表面処理剤組成物 - Google Patents

半導体基板の表面処理方法、及び表面処理剤組成物 Download PDF

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Publication number
WO2021235476A1
WO2021235476A1 PCT/JP2021/018945 JP2021018945W WO2021235476A1 WO 2021235476 A1 WO2021235476 A1 WO 2021235476A1 JP 2021018945 W JP2021018945 W JP 2021018945W WO 2021235476 A1 WO2021235476 A1 WO 2021235476A1
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group
surface treatment
pattern
general formula
carbon atoms
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PCT/JP2021/018945
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English (en)
French (fr)
Japanese (ja)
Inventor
雄三 奥村
由季 福井
彩織 塩田
貴陽 照井
創一 公文
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Central Glass Co Ltd
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Central Glass Co Ltd
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Priority to JP2022524512A priority Critical patent/JP7727202B2/ja
Priority to EP21809701.2A priority patent/EP4155376A4/en
Priority to US17/999,361 priority patent/US20230282473A1/en
Priority to KR1020227044864A priority patent/KR20230015958A/ko
Priority to CN202180036504.7A priority patent/CN115668459B/zh
Publication of WO2021235476A1 publication Critical patent/WO2021235476A1/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/20—Cleaning during device manufacture
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/20—Cleaning during device manufacture
    • H10P70/23—Cleaning during device manufacture during, before or after processing of insulating materials
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass

Definitions

  • the present invention relates to a surface treatment method for a semiconductor substrate and a surface treatment agent composition.
  • Patent Document 1 the technique described in Patent Document 1 is known.
  • Patent Document 1 the surface of a dummy substrate having a SiO 2 film or a SiN film formed on the Si substrate is surface-treated separately from the Si substrate on which the Si pillar pattern is formed on the entire surface, and a dummy having no pattern is provided.
  • a method for evaluating the water contact angle of the substrate is described (Example of Patent Document 1).
  • the surface of the pattern-forming region can be surface-treated, and the surface of the pattern-non-forming region can be surface-treated 2-
  • the contact angle with respect to propanol hereinafter referred to as IPA contact angle
  • the contact angle with pure water hereinafter referred to as water contact angle
  • the main surface of the semiconductor substrate having a pattern forming region in which a pattern having a concavo-convex structure having a pattern dimension of 30 nm or less is formed and a pattern non-forming region in which the pattern is not formed is processed on the main surface of the substrate. It ’s a processing method, A surface treatment step of bringing a surface treatment agent composition containing a silylating agent into contact with the pattern forming region and the pattern non-forming region of the main surface of the semiconductor substrate is included.
  • the IPA contact angle for 2-propanol is 2 ° or more at room temperature 25 ° C and / or
  • the water contact angle with respect to pure water is 50 ° or more at room temperature of 25 ° C.
  • the main surface of the semiconductor substrate having a pattern forming region in which a pattern having a concavo-convex structure having a pattern dimension of 30 nm or less is formed and a pattern non-forming region in which the pattern is not formed is processed on the main surface of the substrate.
  • a surface treatment agent composition used for this purpose Contains a silylating agent
  • the IPA contact angle required by the following procedure is 2 ° or more, and / or The water contact angle required by the following procedure is 50 ° or more.
  • a surface treatment agent composition is provided. (procedure) The surface treatment agent composition is brought into contact with the pattern-forming region and the pattern-non-forming region on the main surface of the semiconductor substrate.
  • the contact angle for 2-propanol was measured at room temperature of 25 degrees, and the value was taken as the IPA contact angle (°).
  • the contact angle with pure water is measured at room temperature of 25 degrees, and the value is taken as the water contact angle (°).
  • a surface treatment method for a semiconductor substrate having excellent manufacturing controllability and manufacturing stability and a surface treatment agent composition used thereof.
  • a pattern forming region in which a pattern having a concavo-convex structure having a pattern dimension of 30 nm or less is formed and a pattern non-forming region in which a pattern is not formed are formed on the main surface of the substrate.
  • This treatment method includes a surface treatment step of bringing the surface treatment agent composition containing a silylating agent into contact with the pattern forming region and the pattern non-forming region on the main surface of the semiconductor substrate, and the pattern non-forming region after the surface treatment step.
  • the IPA contact angle for 2-propanol on the surface is 2 ° or more at room temperature 25 ° C.
  • / or the water contact angle for pure water is 50 ° or more at room temperature 25 ° C.
  • a smooth dummy substrate surface is surface-treated with a surface treatment composition to evaluate the water contact angle, and a separately patterned substrate surface is evaluated.
  • a method of surface-treating with a surface-treating composition to evaluate the collapse-free rate of the pattern In order to confirm whether the specified water repellency is exhibited, it is necessary to separately evaluate the water contact angle using a dummy smooth substrate, and a more efficient manufacturing method (simplification of process control) is desired. The present inventors have found that this is the case.
  • the processing method of the present embodiment is a semiconductor substrate having a structure in which a smooth pattern non-forming region in which a pattern is not formed is provided around an orientation flat or a notch, an outer peripheral portion of a wafer, or the like.
  • This is a more efficient manufacturing method in which the contact angle is evaluated in the pattern non-forming region of the substrate and the collapse free rate is evaluated in the pattern forming region in which the pattern is formed. That is, compared to the conventional complicated manufacturing method in which the water contact angle is separately evaluated using a dummy smooth substrate, the manufacturing method of the present disclosure does not require evaluation of the dummy smooth substrate, and is a semiconductor substrate to be surface-treated.
  • the area of the pattern non-formation region per measurement point contact angle 200 mm 2 or more 2 or more preferably preferably 300 mm, more preferably 350 mm 2 or more, particularly preferably 400 mm 2 or more ..
  • IPA isopropanol
  • second rinse solution described later
  • the IPA contact angle of the surface treatment agent layer formed by the surface treatment is larger, and / or the surface treatment agent layer formed by the surface treatment, in order to further reduce the amount of water.
  • the present inventors have found that a larger water contact angle is desired.
  • the rinse solution after the surface treatment (“second rinse solution” described later) is sequentially rinsed with water and IPA (for example, “surface treatment ⁇ water rinse ⁇ IPA rinse” or the like.
  • IPA for example, “surface treatment ⁇ water rinse ⁇ IPA rinse” or the like.
  • the present inventors have found that there are “surface treatment-> IPA rinse-> water rinse”, etc.), and in such an embodiment, it is desired that the IPA contact angle and the water contact angle be larger.
  • the processing method of another embodiment of the present invention is The main surface of the semiconductor substrate having a pattern forming region in which a pattern having a concavo-convex structure having a pattern dimension of 30 nm or less is formed and a pattern non-forming region in which the pattern is not formed is processed on the main surface of the substrate.
  • the modified state on the surface of the semiconductor substrate can be evaluated using the IPA contact angle and the water contact angle as indexes, and if it is determined that one or both of these are equal to or higher than a predetermined value, the subsequent modification is performed.
  • the substrate processing process can proceed.
  • Subsequent processes include, for example, a second rinsing step, a drying step, a removing step, a known substrate surface treatment that has not yet been carried out, and the like. If the value is not equal to or higher than the predetermined value, the evaluation step may be carried out after the surface treatment step is carried out again. For this reason, it is not necessary to evaluate the contact angle using a dummy substrate, which has been performed separately, and it is possible to determine the progress of the process in the production line, which facilitates manufacturing controllability. Further, after the process is advanced, the pattern collapse in the pattern forming region can be suppressed, so that the manufacturing stability can be improved.
  • the IPA contact angle is 2 ° or more, preferably 3 ° or more at room temperature of 25 ° C. and / or
  • the water contact angle is 50 ° or more, preferably 55 ° or more, more preferably 60 ° or more at room temperature of 25 ° C.
  • the IPA contact angle may be, for example, 10 ° or less
  • the water contact angle may be, for example, 110 ° or less, or 99 ° or less.
  • the IPA contact angle and the water contact angle can be measured on the surface of the surface treatment agent layer formed in the pattern non-forming region by the surface treatment step.
  • the measurement timing after the surface treatment may be immediately after the surface treatment step of bringing the surface treatment agent composition into contact with the main surface of the semiconductor substrate, immediately after the post-rinse step performed after the surface treatment step, or after drying.
  • the measurement may be performed immediately after the process.
  • the timing of measuring the contact angle may be used. At least one may be adopted from these timings.
  • immediately after or immediately before means within 24 hours, preferably within 2 hours, particularly preferably within 30 minutes.
  • the standard deviation of the IPA contact angle at a predetermined 10 positions in the pattern non-forming region can be configured to be, for example, 2 ° or less. Further, the difference between the maximum value and the minimum value of the IPA contact angle can be configured to be, for example, 5 ° or less. Similarly, the standard deviation of the water contact angle at 10 predetermined locations in the pattern non-forming region can be configured to be, for example, 2 ° or less. Further, the difference between the maximum value and the minimum value of the water contact angle can be configured to be, for example, 5 ° or less.
  • a pattern forming region in which a pattern having a concavo-convex structure having a pattern dimension of 30 nm or less is formed and a pattern non-forming region in which the pattern is not formed are formed on the main surface of the substrate. It is used to treat the main surface of a semiconductor substrate having and.
  • Such a surface treatment agent composition contains a silylating agent, and the IPA contact angle determined by the following procedure is 2 ° or more, and / or the water contact angle determined by the following procedure. Is configured to be 50 ° or more.
  • the IPA contact angle and the water contact angle are determined by the following procedure.
  • the surface treatment agent composition is brought into contact with the pattern-forming region and the pattern-non-forming region on the main surface of the semiconductor substrate. After contacting the surface treatment agent composition, with respect to the surface of the pattern non-forming region, The contact angle when 2-propanol was used was measured at room temperature of 25 degrees, and the value was taken as the IPA contact angle (°). The contact angle when pure water is used is measured at room temperature of 25 degrees, and the value is taken as the water contact angle (°).
  • the IPA contact angle or water contact angle is set with respect to the surface of the substrate in the non-patterned region, specifically, the surface of the surface treatment agent layer formed in the non-patterned region, when the semiconductor substrate is placed on a horizontal table. Then, at room temperature of 25 ° C., 1 ⁇ l of 2-propanol or pure water droplets are dropped, and then the value of the static contact angle after 5 seconds is used.
  • the above-mentioned procedure for measuring the contact angle is usually used to evaluate the characteristics of the surface treatment agent composition.
  • the measurement temperature of the contact angle is either 23 degrees ⁇ 5 degrees
  • the droplet amount is 0.1 ⁇ l to 5 ⁇ l
  • the measurement timing is 0.1 seconds to 30 after the droplet is dropped. It is permissible to adopt the above-mentioned contact angle measurement procedure in which one point selected from any of the within seconds is applied to the measurement conditions.
  • the IPA contact angle and / or the water contact angle may be obtained. It is possible to control. Among these, for example, it is desirable to appropriately select the type of silylating agent and other components, mix the composition components, and use them immediately after preparation, so that the above IPA contact angle and / or water contact angle is desired. It is mentioned as an element to make the numerical range of.
  • the surface treatment method using the surface treatment agent composition of the present embodiment it is possible to realize a method for manufacturing a semiconductor substrate having excellent manufacturing controllability and manufacturing stability.
  • the main surface of the semiconductor substrate is patterned, pre-rinsed (first rinse), surface-treated with a surface treatment agent composition, post-rinse (second rinse), and dried.
  • first rinse pre-rinsed
  • second rinse post-rinse
  • examples thereof include a process, a method of removing the surface treatment agent layer, and the like.
  • FIG. 1 is a top view seen from a direction perpendicular to the main surface 12 of the substrate 10 (semiconductor substrate).
  • FIG. 2 is a schematic view of a cross-sectional view of the substrate 10 in a predetermined direction.
  • 3A to 3C are schematic cross-sectional views of a process in the process of manufacturing a semiconductor substrate.
  • a substrate 10 having a pattern (concave and convex structure 20) formed on the main surface 12 is prepared.
  • the following method which is an example of the method of forming the uneven structure 20 on the surface of the substrate 10, may be used.
  • a resist is applied to the surface of the wafer, and then the resist is exposed to the resist through a resist mask, and the exposed resist or the unexposed resist is removed to prepare a resist having a desired uneven pattern.
  • a resist having an uneven pattern can also be obtained by pressing a mold having a pattern against the resist.
  • the wafer is etched. At this time, the substrate surface corresponding to the concave portion of the resist pattern is selectively etched.
  • a wafer (substrate 10) having an uneven structure 20 on the surface is obtained.
  • the wafer on which the concavo-convex structure 20 is formed and the material of the concavo-convex structure 20 are not particularly limited.
  • various wafers such as a silicon wafer, a silicon carbide wafer, a wafer composed of a plurality of components containing silicon elements, a sapphire wafer, and various compound semiconductor wafers can be used.
  • the material of the concave-convex structure 20 is selected from the group consisting of Si, Ti, Ge, W, and Ru, and oxides, nitrides, nitrogen oxides, carbides, and carbonized oxides containing one or more of these. It may contain one or more.
  • silicon-based materials such as silicon oxide, silicon nitride, polycrystalline silicon, single-crystal silicon, and silicon germanium
  • metal-based materials such as titanium nitride, tungsten, ruthenium, tantalum nitride, and tin, and each of them are used.
  • a combined material, a resist (photoresist) material, or the like can be used.
  • the substrate 10 of FIG. 1 has a pattern forming region 30 in which a pattern (concave and convex structure 20) is formed and a pattern non-forming region 32 in which a pattern is not formed on the main surface 12.
  • the substrate 10 of FIG. 1 may have a notch 14 formed in a part of the peripheral edge portion.
  • the notch 14 may be formed with a linear notch called an orientation flat indicating the direction of the crystal axis or a V-shaped notch called a notch for positioning in an exposure apparatus or the like.
  • the pattern forming region 30 is a region in which one or more uneven structures 20 are formed when viewed from a direction perpendicular to the main surface 12, that is, in a top view.
  • the pattern forming region 30 may include an element forming region in which one or more semiconductor elements are formed.
  • the uneven structure 20 is, for example, one or more structures arranged along the vertical direction of the main surface 12, and / or one or more structures arranged along the horizontal direction orthogonal to the vertical direction. It may be composed of a three-dimensional structure having a body.
  • At least a part of a logic device or a memory device may be configured, for example, a FinFET, a nanowire FET, a nanosheet FET, or another multigate FET, a three-dimensional memory. Examples include cells.
  • the pattern non-forming region 32 is a region formed on at least a part of the outer circumference of the pattern forming region 30 or the entire outer circumference in the top view.
  • the pattern non-forming region 32 may be formed continuously with each other or may be divided into a plurality of portions.
  • the pattern non-forming region 32 has a smooth smooth surface region in which the uneven structure 20 is not formed, at least in part.
  • One or two or more cut regions for dicing may be formed in the pattern forming region 30 and / or between the pattern forming region 30 and the pattern non-forming region 32.
  • FIG. 2 is a cross-sectional view showing an example of the concave-convex structure 20.
  • the pattern dimension of the concave-convex structure 20 is at least one width direction dimension in the in-plane direction of the main surface 12 and / or at least one height direction dimension in the direction perpendicular to the main surface 12. Can be defined as.
  • the cross-sectional structure in the thickness direction of the substrate
  • the width and height of the pattern at least one of the width and height of the pattern, or in the three-dimensional structure (three-dimensional coordinates of XYZ) in the pattern of the uneven structure 20, the width thereof.
  • the pattern dimension of at least one of (length in the X-axis direction), height (length in the Y-axis direction), and depth (length in the Z-axis direction) may be, for example, 30 nm or less, or 20 nm or less. It may be 10 nm or less. This may be the spacing between the patterns. Even when the substrate 10 having such a fine concavo-convex structure 20 is used, the surface treatment agent composition of the present embodiment can be applied.
  • Such a surface treatment agent composition is suitable, for example, for surface treatment of a substrate 10 having a concavo-convex structure 20 having a pattern size of 30 nm or less, preferably 20 nm or less.
  • the aspect ratio of the convex portion 22 may be, for example, 3 or more, 5 or more, or 10 or more. Even in the uneven structure 20 having the convex portion 22 having a fragile structure, the pattern collapse can be suppressed. On the other hand, the aspect ratio of the convex portion 22 is not particularly limited, but may be 100 or less. The aspect ratio of the convex portion 22 is represented by a value obtained by dividing the height of the convex portion 22 by the width of the convex portion 22.
  • the substrate 10 may have a bevel region 50 formed at least a part of the end portion of the substrate 10.
  • the substrate 10 in the bevel region 50 may be provided with an inclined surface (bevel) formed on the main surface 12, for example, a top edge 51, an upper bevel 52, a front shoulder 53, an end surface 54, and a lower bevel 55.
  • an inclined surface bevel
  • the main surface 12 of the substrate 10 may be brought into contact with the aqueous cleaning solution (cleaning step).
  • the aqueous cleaning solution include water, alcohol, an aqueous solution of ammonium hydroxide, an aqueous solution of tetramethylammonium, an aqueous solution of hydrochloric acid, an aqueous solution of hydrogen peroxide, an aqueous solution of sulfuric acid, and an organic solvent. These may be used alone or in combination of two or more.
  • the cleaning step may be performed once or twice or more before the surface treatment step or the first rinsing step. Other steps may be included between the plurality of cleaning steps and between the cleaning step and the surface treatment step.
  • the main surface 12 of the substrate 10 may be brought into contact with the first rinsing solution (first rinsing step).
  • a cleaning solution different from the aqueous cleaning solution can be used, for example, water, an organic solvent, a mixture thereof, or at least one of an acid, an alkali, a surfactant, and an oxidizing agent. Examples include those in which the above is mixed.
  • the organic solvent used in the first rinse solution include hydrocarbons, esters, ethers, ketones, halogen element-containing solvents, sulfoxide-based solvents, alcohols, polyhydric alcohol derivatives, nitrogen element-containing solvents and the like. Be done. Among these, it is preferable to use at least one selected from alcohols having 3 or less carbon atoms such as methanol, 1-propanol, and 2-propanol (isopropanol) as the organic solvent.
  • a plurality of types may be used as the first rinse solution.
  • rinsing can be performed in the order of a solution containing an acid aqueous solution or an alkaline aqueous solution ⁇ an organic solvent.
  • an aqueous cleaning solution may be added, and the solution may be carried out in the order of an acid aqueous solution or an alkaline aqueous solution ⁇ an aqueous cleaning solution ⁇ an organic solvent.
  • the first rinsing step may be performed once or more than once after the cleaning step or before the surface treatment step. Other steps may be included between the plurality of first rinsing steps and between the first rinsing step and the surface treatment step.
  • the surface treatment agent composition 60 of the present embodiment is brought into contact with the main surface 12 of the substrate 10 (surface treatment agent composition). It is preferable to supply the liquid surface treatment agent composition 60 to the uneven structure 20 formed on the surface of the substrate 10. At this time, it may be supplied so as to fill a part or all of the concave portion 24 of the concave-convex structure 20.
  • the surface treatment agent composition 60 may be supplied in a state where the first rinse solution or the aqueous cleaning solution is held on the main surface 12. That is, by substituting the first rinsing solution or the aqueous cleaning solution with the surface treatment agent composition 60, the surface treatment step is performed before the surface of the uneven structure 20 on the main surface 12 of the substrate 10 becomes dry. Is possible.
  • a known means can be used.
  • the composition is supplied near the center of rotation while the wafers are held substantially horizontally and rotated, and the unevenness of the wafer is uneven.
  • a single-wafer method typified by a spin method (spin coating method) in which the cleaning liquid held in the pattern is replaced and the composition is filled is preferable, and a plurality of wafers are immersed in the composition tank and the unevenness of the wafers is formed.
  • a batch method or the like may be used in which the cleaning liquid or the like held in the pattern is replaced and the composition is filled.
  • 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. If necessary, known means such as heating treatment, decompression treatment, and drying treatment may be applied to the surface treatment agent composition 60 on the main surface 12 to promote the formation of the surface treatment agent layer 70. good.
  • the surface treatment agent layer 70 is formed on the main surface 12 of the substrate 10 at least in the pattern forming region 30 and the pattern non-forming region 32.
  • the surface treatment agent layer 70 may be formed on the main surface 12 in the bevel region 50, or may be formed on the entire main surface 12.
  • the main surface 12 on which the surface treatment agent layer 70 is formed may be brought into contact with the second rinsing liquid (second rinsing step).
  • the second rinsing solution those exemplified for the first rinsing solution can be used.
  • a plurality of types may be used as the second rinse solution.
  • rinsing can be performed in the order of water ⁇ an organic solvent such as isopropanol or organic solvent such as isopropanol ⁇ water.
  • the second rinsing step may be performed once or twice or more after the surface treatment step. Other steps may be included between the plurality of second rinsing steps and between the second rinsing step and the surface treatment step.
  • a drying step of drying the main surface 12 of the substrate 10 may be performed.
  • the drying step the liquid existing on the main surface 12 of the substrate 10 can be removed.
  • known means such as spin drying method, IPA (2-propanol) steam drying, marangoni drying, heat drying, warm air drying, vacuum drying and the like may be used.
  • the drying step may be performed once or twice or more, for example, after the surface treatment step or after the second rinsing step.
  • the drying step and the second rinsing step may be repeated alternately.
  • the surface treatment agent layer 70 on the main surface 12 of the substrate 10 may be removed (removal step).
  • the removing means include heating, UV irradiation, ozone exposure, plasma irradiation, corona discharge and the like.
  • treatment with a concentrated fluid such as a supercritical fluid (which may contain an acid, a base or an oxidizing agent) or steam treatment may be performed. These may be used alone or in combination of two or more. These treatments may be performed under atmospheric pressure or reduced pressure.
  • the manufacturing method shown in FIG. 3 targets a wafer pattern, but the present invention is not limited to this.
  • the method for producing a substrate of the present embodiment it is possible to suppress the resist pattern from collapsing by using the surface treatment agent composition of the present invention in the cleaning / drying step of the resist pattern.
  • the manufacturing method is not limited to this, and may be carried out after various treatments carried out on the uneven structure 20.
  • a method for manufacturing a substrate one or a combination of two or more known treatments may be used in addition to the above steps. For example, after the above removing step, a surface treatment such as plasma treatment may be performed.
  • the surface treatment agent composition of the present embodiment contains a silylating agent.
  • a silylating agent a known silylating agent can be used.
  • a silicon compound represented by the following general formula [1] is used. These may be used alone or in combination of two or more.
  • R 1 is an organic group containing a hydrocarbon group having 1 to 18 carbon atoms, which may be replaced with a fluorine element in part or all of the hydrogen elements independently of each other.
  • X is a monovalent organic group in which the element bonded to the Si element is nitrogen, oxygen, carbon, or halogen independently of each other, a is an integer of 1 to 3, and b is 0 to 2. It is an integer, and the sum of a and b is 1 to 3.
  • R 1 in the above general formula [1] contains a silicon element
  • the structure of the general formula [1-1] shown below may be adopted.
  • R 1 (however, this R 1 does not contain a silicon element) and X are the same as 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-(CH 2 ) p- is halogen-substituted. May be.
  • the monovalent organic group in which the element bonded to the Si element is nitrogen, oxygen or carbon includes not only hydrogen, carbon, nitrogen and oxygen elements but also silicon, sulfur and halogen elements. Etc. may be included.
  • All hydrogen elements may be replaced with fluorine elements, which are monovalent hydrocarbon groups having 1 to 8 carbon atoms and groups selected from the group consisting of fluorine elements), and the following general formula [1. -2] Substituents having the structure of (In the general formula [1-2], R 5 are each independently of one another, a divalent hydrocarbon of some or all of the hydrogen element is carbon atoms, which may have been replaced by fluorine element 1-8 a group), -.
  • N C ( NR 6 2)
  • -N C (NR 6 2)
  • R 6 are each independently of one another, hydrogen group, -C ⁇ N group , -NO 2 and even if some or all of the hydrogen elements are selected from hydrocarbon groups that may be replaced by fluorine elements, the hydrogen groups may have oxygen and / or nitrogen atoms.
  • Good -N (R a1 ) (R a2 ) (where R a1 represents a hydrogen atom or a saturated or unsaturated alkyl group, and R a2 is a saturated or unsaturated alkyl group, saturated or unsaturated cyclo.
  • R a3 indicates 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 independently represent hydrogen atoms or organic groups, respectively , and the total number of carbon atoms contained in R a4 , R a5 and R a6 is one or more), -N (R a7).
  • R a8 (Here, R a7 indicates a hydrogen atom, a methyl group, a trimethylsilyl group, or a dimethylsilyl group, and R a8 is a hydrogen atom, a saturated or unsaturated alkyl group, and fluorine-containing. It indicates an alkyl group or a trialkylsilylamino group.), Etc.
  • Examples of the silylating agent in which X in the above general formula [1] is a monovalent organic group in which the element bonded to the Si element is nitrogen include CH 3 Si (NH 2 ) 3 , C 2 H 5 Si. (NH 2 ) 3 , C 3 H 7 Si (NH 2 ) 3 , C 4 H 9 Si (NH 2 ) 3 , C 5 H 11 Si (NH 2 ) 3 , C 6 H 13 Si (NH 2 ) 3 , C 7 H 15 Si (NH 2 ) 3 , C 8 H 17 Si (NH 2 ) 3 , C 9 H 19 Si (NH 2 ) 3 , C 10 H 21 Si (NH 2 ) 3 , C 11 H 23 Si ( NH 2 ) 3 , C 12 H 25 Si (NH 2 ) 3 , C 13 H 27 Si (NH 2 ) 3 , C 14 H 29 Si (NH 2 ) 3 , C 15 H 31 Si (NH 2 ) 3 , C 16 H 33 Si (NH 2 ) 3 , C 17 H 35 Si (
  • R 5 are each independently of one another, a divalent hydrocarbon of some or all of the hydrogen element is carbon atoms, which may have been replaced by fluorine element 1-8 is a group for example, N- (trimethylsilyl) N, N-difluoromethane-1,3-bis (sulfonyl) imide), -.
  • N C ( NR 6 2) 2
  • -N C (NR 6 2) R 6
  • R 6 is a hydrocarbon in which hydrogen groups, -C ⁇ N groups, -NO 2 groups, and some or all hydrogen elements may be replaced with fluorine elements independently of each other. Selected from hydrogen groups, the hydrocarbon group may have an oxygen atom and / or a nitrogen atom, eg 2-trimethylsilyl-1,1,3,3-tetramethylguanidine), -N (R).
  • R a1 indicates a hydrogen atom or a saturated or unsaturated alkyl group
  • R a2 is a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a saturated or unsaturated heterocyclo. Indicates an alkyl group.
  • 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).
  • R a3 indicates a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a trimethylsilyl group, or a dimethylsilyl group
  • R a4 , R a5, and R a6 are independent of each other.
  • hexamethyldisilazane N-methylhexamethyldisilazane, 1, 1,3,3-Tetramethyldisilazan, 1,3-dimethyldisilazane, 1,3-di-N-octyltetramethyldisilazan, 1,3-divinyltetramethyldisilazan, heptamethyldisilazan, N- Allyl-N, N-bis (trimethylsilyl) amine, 1,3-diphenyltetramethyldisilazane, and 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, nonamethyltrisilazane, pentamethylethyl Disilazan, pentamethylvinyldisilazan, pentamethylpropyldisilazan, pentamethylethyldisilazan, pentamethyl-t-butyldisilazan, penta
  • silylating agent in which X in the general formula [1] is a monovalent organic group in which the element bonded to the Si element is oxygen for example, the amino group (-NH 2 group) of the above-mentioned aminosilane is used.
  • R a9 (where A above indicates O, CHR a10 , CHOR a10 , CR a10 R a10 , or NR a11 , and R a9 , R a10 are independently hydrogen atoms, saturated, or An 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.
  • R a11 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group.
  • R a16 indicates a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a fluorine-containing alkyl group.
  • R a17 has an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group, a phenyl group, a tolyl group, and -O-Si (CH).
  • 3 Shows 3 groups, for example (eg, trimethylsilylsulfonate, trimethylsilylbenzenesulfonate, trimethylsilyltoluenesulfonate, trimethylsilyltrifluoromethanesulfonate, trimethylsilylperfluorobutanesulfonate, bistrimethylsilylsulfate, etc.), -OP (-O-Si).
  • (CH 3 ) 3 ) 2 (for example, tristrimethylsilylphosphite or the like) may be replaced.
  • examples of the silylating agent in which X in the general formula [1] is a monovalent organic group in which the element bonded to the Si element is oxygen include hexamethyldisiloxane and 1,3-diphenyl-1. , 3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,1-triethyl-3,3-dimethyldisiloxane, 1,1,3,3-tetra-n-octyldimethyl Disiloxane, bis (nonafluorohexyl) tetramethyldisiloxane, 1,3-bis (trifluoropropyl) tetramethyldisiloxane, 1,3-di-n-butyltetramethyldisiloxane, 1,3-di-n -Octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane, 1,3
  • X in the general formula [1] is a monovalent organic group in which the element bonded to the Si element is carbon
  • the amino group (-NH 2 group) of the above-mentioned aminosilane is used.
  • X in the above general formula [1] is a monovalent organic group in which the element bonded to the Si element is a halogen
  • the amino group (-NH 2 group) of the above-mentioned aminosilane is used. Is replaced with a chloro group, a bromo group, an iodo group (for example, chlorotrimethylsilane, bromotrimethylsilane, etc.) and the like.
  • the cyclic silazane compound can be included as the silylating agent.
  • examples of the cyclic silazane compound include 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane and 2,2,6,6-tetramethyl-2,6-disila-1-aza.
  • Cyclic disilazane compounds such as cyclohexane; cyclic trisilazane compounds such as 2,2,4,4,6,6-hexamethylcyclotrisilazane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane; Cyclic tetrasilazane compounds such as 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane; and the like.
  • the surface treatment agent composition comprises a compound A described later, an acid imidized product, a nitrogen-containing compound, a nitrogen-containing heterocyclic compound containing no silicon atom, and silylation as a catalyst for the silylating agent. It can contain one or more selected from the group consisting of heterocyclic compounds.
  • the catalyst promotes the reaction between the main surface and the silylating agent, or enhances the liquid-repellent performance of the surface treatment agent layer to be formed, and is itself or a modified product on the surface. It may form a part of the treatment agent layer.
  • the concentration of the catalyst may be, for example, 0.005% by mass or more and 20% by mass or less, or 0.05% by mass or more and 15% by mass or less with respect to 100% by mass of the surface treatment agent composition.
  • compound A examples include, for example, trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyltrifluoromethanesulfonate, butyldimethylsilyltrifluoroacetate, butyldimethylsilyltrifluoromethanesulfonate, and hexyldimethylsilyl.
  • Examples thereof include trifluoroacetate, hexyldimethylsilyltrifluoromethanesulfonate, octyldimethylsilyltrifluoroacetate, octyldimethylsilyltrifluoromethanesulfonate, decyldimethylsilyltrifluoroacetate, and decyldimethylsilyltrifluoromethanesulfonate, which are selected from these.
  • the above-mentioned compound A may correspond to the above-mentioned silylating agent, but when used as a catalyst, it means that it is used in combination with other silylating agents other than compound A.
  • the compound A is one or more acetic acids selected from the group consisting of the silicon compound represented by the following general formula [2], trifluoroacetic acid, trifluoroacetic acid anhydride, trifluoromethanesulfonic acid, and trifluoromethanesulfonic acid anhydride. It may be obtained by reacting with sulfonic acid.
  • the surplus silicon compound represented by the following general formula [2] that remains without being consumed in this reaction can be used as the silylating agent together with the compound A obtained in the reaction.
  • the silicon compound represented by the following general formula [2] is, for example, 0.2 to 100,000 mol times, preferably 0.5 to 50,000 mol times, more preferably 1 in terms of molar ratio with respect to the above acetic acid or sulfonic acid.
  • the reaction may be carried out at a factor of 10,000 mol.
  • the compound A is a group consisting of a sulfonic acid represented by the following general formula [3], an anhydride of the sulfonic acid, a salt of the sulfonic acid, and a sulfonic acid derivative represented by the following general formula [4]. It may be at least one selected from.
  • R 8- S ( O) 2 OH [3]
  • R 8 is a group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms and a hydroxyl group, in which some or all hydrogen elements may be replaced with fluorine elements. It is a group selected from.
  • R 8 '-S ( O) 2 O-Si (H) 3-r (R 9) r
  • R 8 '-S ( O) 2 O-Si (H) 3-r (R 9) r
  • R 8 '-S ( O) 2 O-Si (H) 3-r (R 9) r
  • R 8 '-S ( O) 2 O-Si (H) 3-r (R 9) r
  • R 8 '-S ( O) 2 O-Si (H) 3-r (R 9) r
  • R 8 ' is a monovalent hydrocarbon group having some or all of the hydrogen element is carbon atoms, which may have been replaced by fluorine element 1 ⁇ 8
  • R 9 is , Each of which is at least one group selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms, each of which may have some or all of the hydrogen elements replaced with fluorine elements, independently of each other. It is an integer of 1 to 3.
  • the compound A is represented by a sulfonic acid ester represented by the following general formula [5], a sulfonimide represented by the following general formulas [6] and [7], and the following general formulas [8] and [9]. It may be at least one selected from the group consisting of the sulfoneimide derivative to be used, the sulfonmethide represented by the following general formula [10], and the sulfonmethide derivative represented by the following general formula [11].
  • R 13 is a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all hydrogen elements may be replaced with fluorine elements.
  • R 14 is a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen elements may be replaced with fluorine elements independently of each other.
  • R 15 are each independently of one another, some or all of the hydrogen element is carbon atoms, which may have been replaced by fluorine element monovalent 1-18 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.
  • R 16 is a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen elements may be replaced with fluorine elements independently of each other.
  • R 17 is a monovalent hydrocarbon group having 1 to 18 carbon atoms, and some or all of the hydrogen elements may be replaced with fluorine elements independently of each other, and u is 1 to 1 to 1.
  • R 18 is a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which some or all hydrogen elements may be replaced with fluorine elements independently of each other. And, it is a group selected from the group consisting of fluorine elements.
  • R 19 is a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen elements may be replaced with fluorine elements independently of each other. and, a group selected from the group consisting of elemental fluorine, R 20 are each independently of one another, some or all of the hydrogen element is carbon atoms, which may have been replaced by fluorine element monovalent 1-18 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.
  • examples of the acid imidized compound include compounds having a chemical structure in which an acid such as carboxylic acid and phosphoric acid is imidized.
  • examples of the above-mentioned nitrogen-containing compound include at least one of the compounds represented by the following general formulas [12] and [13].
  • R 21 -N C (NR 22 2) 2 [12]
  • R 21 -N C (NR 22 2)
  • R 21 is a hydrogen group, -C ⁇ N group, -NO 2 group, alkylsilyl group, and, some or all of the hydrogen elements are replaced with fluorine element It is selected from possible hydrocarbon groups, and the hydrocarbon group may have an oxygen atom and / or a nitrogen atom, but when it contains a nitrogen atom, it shall have an acyclic structure.
  • R 22 is independently selected from hydrogen groups, -C ⁇ N groups, -NO 2 groups, and hydrocarbon groups in which some or all of the hydrogen elements may be replaced with fluorine elements.
  • the hydrocarbon group may have an oxygen atom and / or a nitrogen atom, but when it contains a nitrogen atom, it shall have an acyclic structure.
  • Examples of the above-mentioned nitrogen-containing compound include guanidine, 1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,1,3,3-tetramethylguanidine, and 1,3-diphenylguanidine. , 1,2,3-triphenylguanidine, N, N'-diphenylform amidine, 2,2,3,3,3-pentafluoropropylamidine and the like.
  • examples of the nitrogen-containing heterocyclic compound containing no silicon atom and the silylated heterocyclic compound include at least one of the compounds represented by the following general formulas [14] and [15].
  • R 23 and R 24 are divalent organic groups each independently composed of a carbon element and / or a nitrogen element and a hydrogen element, and the total number of carbon atoms and nitrogen number is In the case of 1 to 9 and 2 or more, carbon elements that do not form a ring may be present.
  • R 25 a part or all of hydrogen and an alkyl group element-1 carbon atoms, which may have been replaced by fluorine element 6, some or all of the hydrogen element fluorine element
  • a trialkylsilyl group having an alkyl group having 1 to 8 carbon atoms may be replaced with an alkenyl group having 2 to 6 carbon atoms, and some or all of the hydrogen elements may be replaced with a fluorine element.
  • Some or all hydrogen elements may be replaced with fluorine elements alkoxy groups and amino groups having 1 to 6 carbon atoms, and some or all hydrogen elements may be replaced with fluorine elements.
  • alkylamino group having 1 to 6 alkyl groups a dialkylamino group having an alkyl group having 1 to 6 carbon atoms in which some or all hydrogen elements may be replaced with a fluorine element, and some or all hydrogens.
  • element aminoalkyl group of the fluorine-carbon atoms which may have been replaced by elements 1-6, a nitro group, a cyano group, a phenyl group, a benzyl group, or a halogen group, R 26, R 27 and R 28 , Each of which is an alkyl group or a hydrogen group having 1 to 6 carbon atoms, in which a part or all of the elemental hydrogen may be replaced with the elemental fluorine element.
  • the above-mentioned nitrogen-containing heterocyclic compound containing no silicon atom may contain a heteroatom other than the nitrogen atom such as an oxygen atom and a sulfur atom in the ring, or may have an aromatic property, and may have two or more.
  • a compound in which a plurality of rings are bonded by a single bond or a polyvalent linking group having a valence of 2 or more may be used. It may also have a substituent.
  • nitrogen-containing heterocyclic compound containing no silicon atom examples include pyridine, pyridazine, pyrazine, pyrimidine, triazine, tetrazine, pyrrol, pyrazole, imidazole, triazole, tetrazole, oxazole, isooxazole, thiazole, isothiazole, and oxal.
  • examples of the above-mentioned silylated heterocyclic compound include a silylated imidazole compound and a silylated triazole compound.
  • examples of the silylated heterocyclic compound include monomethylsilylimidazole, dimethylsilylimidazole, trimethylsilylimidazole, monomethylsilyltriazole, dimethylsilyltriazole, trimethylsilyltriazole and the like.
  • the above-mentioned silylated heterocyclic compound may correspond to the above-mentioned silylating agent, but when used as a catalyst, it means that it is used in combination with other silylating agents other than the silylated heterocyclic compound.
  • the concentration of the silylating agent or the total concentration of the silylating agent and the catalyst is, for example, 0.01% by mass or more with respect to 100% by mass of the surface treatment agent composition. It may be 100% by mass, preferably 0.1% by mass to 50% by mass, and more preferably 0.5% by mass to 30% by mass.
  • the surface treatment agent composition can contain a solvent.
  • the solvent is not particularly limited as long as it dissolves the silylating agent.
  • the solvent include hydrocarbons, esters, ethers, ketones, halogen element-containing solvents, sulfoxide-based solvents, alcohols, carbonate-based solvents, polyhydric alcohol derivatives, nitrogen element-containing solvents, silicone solvents, and thiols.
  • Organic solvents such as are used.
  • hydrocarbons, esters, ethers, halogen element-containing solvents, sulfoxide-based solvents, and derivatives of polyhydric alcohols those having no OH group are preferable. These may be used alone or in combination of two or more.
  • hydrocarbons examples include linear, branched, or cyclic hydrocarbon-based solvents, aromatic hydrocarbon-based solvents, terpinene-based solvents, and the like, and include n-hexane, n-heptane, and n-octane. , N-nonan, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecan, n-octadecan, n-aikosan, and branched hydrocarbons corresponding to their carbon numbers (eg, isododecane).
  • Cyclohexane Methylcyclohexane, Decalin, benzene, Toluene, Xylene, (Ortho-, Meta-, or Para-) diethylbenzene, 1,3,5-trimethylbenzene, Naphthalene, Mesitylene, p-Menthane, o- Mentan, m-menthane, diphenylmenthane, limonene, ⁇ -terpinene, ⁇ -terpinene, ⁇ -terpinene, bornan, norbornan, pinan, ⁇ -pinene, ⁇ -pinene, curan, longi noire, avietan, terpine-based solvents and the like.
  • esters examples include ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-hexyl acetate, n-heptyl acetate.
  • cyclic esters such as a lactone compound may be used.
  • lactone compounds include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -heptanolactone, ⁇ -octanolactone, ⁇ -nonanolactone, ⁇ -decanolactone, ⁇ - Undecanolactone, ⁇ -dodecanolactone, ⁇ -valerolactone, ⁇ -hexanolactone, ⁇ -octanolactone, ⁇ -nonanolactone, ⁇ -decanolactone, ⁇ -undecanolactone, ⁇ -dodecanolactone, ⁇ -hexa There are nolactone and so on.
  • ethers examples include di-n-propyl ether, ethyl-n-butyl ether, di-n-butyl ether, ethyl-n-amyl ether, di-n-amyl ether, ethyl-n-hexyl ether, and di-.
  • Ethers with branched hydrocarbon groups such as n-hexyl ethers, di-n-octyl ethers, and diisopropyl ethers and diisoamyl ethers corresponding to their carbon atoms, dimethyl ethers, diethyl ethers, methyl ethyl ethers, methyl cyclopentyl ethers.
  • ketones examples include acetone, acetylacetone, methylethylketone, methylpropylketone, methylbutylketone, 2-heptanone, 3-heptanone, cyclohexanenon, isophorone and the like.
  • halogen element-containing solvent examples include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, and hexafluorobenzene, 1,1,1,3,3-pentafluorobutane, and octa.
  • perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, and hexafluorobenzene, 1,1,1,3,3-pentafluorobutane, and octa.
  • Fluorocarbons such as fluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeolola H (manufactured by Zeon Japan), methylperfluoropropyl ether, methylperfluoroisobutyl ether, methylperfluorobutyl ether, ethylperfluorobutyl ether, ethylper Hydrofluoroethers such as fluoroisobutyl ether, methylperfluorohexyl ether, ethylperfluorohexyl ether, asahiclin AE-3000 (manufactured by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec7300, Novec7600 (all manufactured by 3M).
  • Chlorocarbons such as tetrachloromethane, hydrochlorocarbons such as chloroform, chlorofluorocarbons such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro- Hydrochlorofluorocarbons such as 1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene, per. Fluoroethers, perfluoropolyethers, etc.
  • Examples of the above sulfoxide solvent include dimethyl sulfoxide and the like.
  • Examples of the carbonate-based solvent include dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, propylene carbonate and the like.
  • Examples of the above alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-Methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1- Pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2- Methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butano
  • Examples of the above polyhydric alcohol derivatives having no OH group include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate.
  • nitrogen element-containing solvent examples include formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, and the like.
  • N-dimethyl-2-imidazolidinone 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, diethylamine, triethylamine, pyridine and the like.
  • silicone solvent examples include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and the like.
  • Examples of the above thiols include 1-hexanethiol, 2-methyl-1-pentanethiol, 3-methyl-1-pentanethiol, 4-methyl-1-pentanethiol, and 2,2-dimethyl-1-butanethiol.
  • the solvent preferably contains an aprotic solvent.
  • the content of the aprotic solvent is, for example, 80% by mass or more, preferably 90% by mass or more, in 100% by mass of the solvent. It is more preferable that the solvent is an aprotic solvent, that is, the solvent contains an aprotic solvent in an content of 100% by mass in 100% by mass of the solvent.
  • aprotic solvent examples include hydrocarbons, esters, ethers, ketones, halogen element-containing solvents, sulfoxides, carbonate solvents, polyhydric alcohol derivatives, nitrogen element-containing solvents, silicone solvents and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use one or more selected from the group consisting of derivatives of polyhydric alcohols, hydrocarbons, and ethers.
  • derivatives of polyhydric alcohols are preferable, for example, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol.
  • propylene carbonate a linear or branched hydrocarbon solvent having 6 to 12 carbon atoms
  • p-menthane diphenylmenthane, limonene, terpinene, bornane, norbornane, pinan and the like are also preferable.
  • the silylating agent is hexamethyldisilazane, heptamethyldisilazane, N- (trimethylsilyl) dimethylamine, bis (dimethylamino) dimethylsilane, and the like.
  • the surface treatment agent composition may not contain water or may contain water in a content of 2% by mass or less in 100% by mass of the surface treatment agent composition. As described above, it is possible to use a surface treatment agent composition that does not substantially contain water.
  • the surface treatment agent composition may contain components other than the above-mentioned components as long as the object of the present invention is not impaired.
  • examples of other components include oxidizing agents such as hydrogen peroxide and ozone, surfactants, and antioxidants such as BHT.
  • the surface treatment agent composition of the present embodiment is obtained by mixing each of the above-mentioned components.
  • the obtained mixed solution may be purified by using an adsorbent, a filter or the like, if necessary. Further, each component may be purified in advance by distillation and purified using an adsorbent, a filter or the like.
  • TMSDMA and PGMEA were mixed at a liquid temperature of 25 ° C. and stirred for 1 minute. Further, a surface treatment agent containing 0.1% by mass of trimethylsilyltrifluoroacetate (TMSTFA) as compound A and 1% by mass of MTSDMA as a silylating agent by adding trifluoroacetic acid (TFA) and reacting with TMSMA. Composition 2 was prepared. The surface treatment agent composition 2 immediately after preparation was used for the surface treatment described later.
  • TMSTFA trimethylsilyltrifluoroacetate
  • TMSMA trifluoroacetic acid
  • the surface treatment agent composition 3 was prepared by preparing the surface treatment agent composition 2 in the same manner as that of the surface treatment agent composition 2 except that TEMSMA was replaced with hexmethyldisilazane (HMDS). The surface treatment agent composition 3 immediately after preparation was used for the surface treatment described later.
  • HMDS hexmethyldisilazane
  • a convex structure having a plurality of substantially columnar convex portions having an aspect ratio of 22 and a pattern width of 19 nm in a cross-sectional view at a pitch of 90 nm (total distance between the widths of the convex portions and the adjacent intervals of the convex portions) is formed on the surface.
  • a silicon substrate was prepared having a smooth region formed and no pattern formed on the outer peripheral portion thereof.
  • the portion having a convex structure is referred to as a “pattern forming region”, and the smooth portion in which a pattern is not formed is referred to as a “pattern non-forming region”.
  • the IPA contact angle and the water contact angle, which will be described later, were measured in the pattern non-forming region, and the area of the pattern non-forming region per measurement point of the contact angle at this time was about 250 mm 2 .
  • ⁇ Substrate surface treatment> To the surface of the substrate was subjected to dry cleaning by UV / O 3 irradiation. The surfaces of the pattern-forming region and the pattern-non-forming region of the substrate were oxidized to silicon oxide. Subsequently, the substrate was placed on a spin coater, and while rotating the substrate at a speed of 200 rpm, 2-propanol (IPA), the surface treatment agent composition shown in Table 1, and IPA in this order at a speed of 200 cc / min. The substrate was discharged, and finally the substrate was dried while discharging N 2 to the substrate.
  • IPA 2-propanol
  • IPA contact angle At room temperature of 25 degrees, the surface-treated silicon substrate was set on a contact angle meter, and about 1 ⁇ L of 2-propanol (IPA) was dropped onto the non-pattern-forming region while the surface-treated silicon substrate was placed on a horizontal table, and 5 seconds later. The droplet state was observed, and the contact angle (°) of IPA at this time was measured as the IPA contact angle.
  • the IPA contact angles are shown in Table 3. (Water contact angle) Using the same substrate used in the above IPA contact angle measurement at a room temperature of 25 degrees, the surface-treated silicon substrate was set on the contact angle meter, and placed on a horizontal table.
  • the surface treatment method according to the embodiment of the present disclosure is separately evaluated using a dummy smooth substrate in order to confirm whether or not a predetermined IPA contact angle and / or a predetermined water contact angle can be developed. This is a more efficient method than the conventional method.
  • Substrate 12 Main surface 14 Notch 16 Back surface 20 Concavo-convex structure 22 Convex 24 Concave 30 Pattern formation area 32 Pattern non-formation area 50 Bevel area 51 Top edge 52 Upper bevel 53 Front shoulder 54 End surface 55 Lower bevel 60 Surface treatment agent composition 70 Surface treatment agent layer

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