Method for manufacturing wafer, surface treatment composition for thermal evaporation, method for using surface treatment composition, vapor composition, and method for manufacturing vapor composition

Abstract

This method for manufacturing a wafer comprises: a step for preparing a wafer having an uneven pattern on a surface thereof; a step for supplying a cleaning liquid to the surface of the wafer and cleaning the surface; and a step for supplying vapor of a surface treatment composition to the surface retaining the cleaning liquid, changing the state of the vapor to a liquid on the surface, replacing at least a portion of the cleaning liquid with the liquid, and forming a water-repellent protective film on at least a portion of the surface. The surface treatment composition includes a prescribed silicon compound and one or two or more aprotic solvents.　

Description

Method for manufacturing a wafer, surface treatment composition for heating and vaporization, method for using the surface treatment composition, vapor composition, and method for manufacturing the vapor composition.

[0001] The present invention relates to a method for manufacturing wafers, a surface treatment composition for heating and vaporization, a method for using the surface treatment composition, a vapor composition, and a method for manufacturing the vapor composition.

[0002] Semiconductor devices for networks and digital consumer electronics are required to be even more high-performance, highly functional, and low-power. Therefore, circuit patterns are becoming smaller, and as miniaturization progresses, pattern collapse is becoming a problem. In semiconductor device manufacturing, cleaning processes are frequently used to remove particles and metal impurities, resulting in cleaning processes accounting for 30-40% of the entire semiconductor manufacturing process. In this cleaning process, as the aspect ratio of patterns increases with the miniaturization of semiconductor devices, the patterns collapse when the gas-liquid interface passes over them after cleaning or rinsing. This phenomenon is called pattern collapse. Because pattern collapse necessitates changes to pattern design and leads to reduced production yield, methods to prevent pattern collapse in the cleaning process are desired.

[0003] It is known that forming a water-repellent protective film on the pattern surface is an effective method for preventing pattern collapse. Since this water-repellency must be achieved without drying the pattern surface, a water-repellent protective film-forming chemical solution capable of making the pattern surface water-repellent is supplied to the pattern surface while it is still holding a cleaning solution, and the cleaning solution is replaced by the chemical solution to form the water-repellent protective film.

[0004] As a type of technology, the technologies described in Patent Documents 1 and 2 are known. The silylating agents used in the examples of Patent Documents 1 and 2 include hexamethyldisilazane (HMDS) and trimethylsilyldimethylamine (TMSMDMA).

[0005] International Publication No. 2012 / 002346, Japanese Patent Publication No. 2018-182112

[0006] An object of the present invention is to provide a vapor of a novel surface treatment composition and a method for manufacturing a wafer using the same.

[0007] According to one aspect of the present invention, there are provided the following method for manufacturing a wafer, a surface treatment composition for heat evaporation, a method for using the surface treatment composition, a vapor composition, and a method for manufacturing the vapor composition.

[0008] 1. A step of preparing a wafer having a concavo-convex pattern on its surface, a step of supplying a cleaning liquid to the surface of the wafer for cleaning, and a step of supplying a vapor of a surface treatment composition to the surface holding the cleaning liquid, changing the state of the vapor into a liquid on the surface, replacing at least a part of the cleaning liquid with the liquid, and forming a water-repellent protective film on at least a part of the surface. A method for manufacturing a wafer, wherein the surface treatment composition includes at least one silicon compound selected from the group consisting of the following general formula [1], the following general formula [2], and the following general formula [3], and one or more aprotic solvents. R ３－ｄ , ｃ , ３－ｃ , ２ , ３ , ３ , ｄ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １ is each independently a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms in which part or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, and X is each independently a monovalent group in which the atom bonded to the Si atom is nitrogen, oxygen, carbon, or halogen (however, when X is a dialkylamino group, the total number of carbon atoms is 5 or more), 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.) (R ２ ｃ Si(H) ３－ｃ ) ３－ｄ NR ３ ｄ [2] (In the above general formula [2], R ２ is each independently a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 5 carbon atoms in which part or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, and R ３Each is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ２ The total number of carbon atoms and R ３ The sum of the total number of carbon atoms is 5 or less, c is an integer from 1 to 3, and d is 0 or 1. (In the above general formula [3], R ４ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Y is independently -[(CR ６ ２ ) ｉ -Si(R ４ａ ) ２ ]- (wherein Si is bonded to N in the general formula [3] above), or-[NR ５ａ -Si(R ４ａａ ) ２ ] ｊ - (However, Si is R ４ａａ It can also bond with N or C, and N is R ５ａ (Other than bonding with Si or C), R ４ａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ４ａａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ａ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ６) 2. A method for manufacturing a wafer as described in 1. The aprotic solvent comprises one or more aprotic solvents A satisfying the following condition A, and the total content of the aprotic solvent A is 70% by mass or more of the total amount of the aprotic solvent A. Condition A: When the boiling point (°C) of at least one of the silicon compounds at 1 atmosphere is PB1, and the boiling point (°C) of the aprotic solvent A at 1 atmosphere is PB2, (PB1 - PB2) ≥ -10°C. 3. 2. A method for manufacturing a wafer as described in 1., wherein in the surface treatment composition, PB1-PB2, which represents the boiling point difference between the silicon compound and the aprotic solvent A, is 0°C or more and 160°C or less. 4. A method for manufacturing a wafer as described in 2. or 3., wherein the boiling point (PB1) of the silicon compound at 1 atmosphere is 90°C or more and 250°C or less. 5. A method for manufacturing a wafer as described in 2. or 3., wherein the boiling point (PB2) of the aprotic solvent A at 1 atmosphere is 90°C or more and 240°C or less. 6. A method for manufacturing a wafer as described in any one of 1. to 5., wherein the cleaning solution contains a protic solvent. 7. A method for manufacturing a wafer as described in any one of 1. to 6., wherein the surface treatment composition does not contain a catalyst, or contains a catalyst in an amount of 5% by mass or less in 100% by mass of the surface treatment composition. 8. 1. to 7. A wafer manufacturing method according to any one of the above, wherein in the step of forming the water-repellent protective film, the angle between the normal vector of the surface of the wafer and the vertical vector is greater than 0° and less than or equal to 180°.9. A wafer manufacturing method according to any one of 1 to 8, wherein in the step of forming the water-repellent protective film, the vapor of the surface treatment composition supplied is obtained by vaporizing a liquid surface treatment composition by at least heat treatment, and the vapor of the surface treatment composition is supplied. 10. A wafer manufacturing method according to any one of 1 to 9, further comprising the step of cleaning at least a portion of the surface of the wafer after the step of forming the water-repellent protective film. 11. A wafer manufacturing method according to any one of 1 to 10, further comprising the step of cleaning at least a portion of the inside of the chamber from which the vapor was supplied after the step of forming the water-repellent protective film. 12. A surface treatment composition for heating and evaporation, used to supply a cleaning solution in vapor form to the surface of a wafer containing a cleaning solution, wherein the surface treatment composition comprises at least one silicon compound selected from the group consisting of the following general formulas [1], [2], and [3], and one or more aprotic solvents. １ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １ Each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having nitrogen, oxygen, carbon, or halogen atoms bonded to the Si atom (provided that when X is a dialkylamino group, the total number of carbon atoms is 5 or more); a is an integer from 1 to 3; b is an integer from 0 to 2; and the sum of a and b is 1 to 3. ２ ｃ Si(H) ３－ｃ ) ３－ｄ NR ３ ｄ [2] (In the above general formula [2], R ２ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 5 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R３ Each is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ２ The total number of carbon atoms and R ３ The sum of the total number of carbon atoms is 5 or less, c is an integer from 1 to 3, and d is 0 or 1. (In the above general formula [3], R ４ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Y is independently -[(CR ６ ２ ) ｉ -Si(R ４ａ ) ２ ]- (wherein Si is bonded to N in the general formula [3] above), or-[NR ５ａ -Si(R ４ａａ ) ２ ] ｊ - (However, Si is R ４ａａ It can also bond with N or C, and N is R ５ａ (Other than bonding with Si or C), R ４ａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ４ａａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ａ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ６(i) is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 9 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, i is 0 to 9, j is 0 to 5, and h is an integer i + 2 × j + 1 (where 1 ≤ h ≤ 10). 13. A method for using a surface treatment composition, comprising the step of supplying the surface treatment composition in vapor form to the surface of a wafer holding a cleaning solution, wherein the surface treatment composition comprises at least one silicon compound selected from the group consisting of the following general formulas [1], [2], and [3], and one or more aprotic solvents. １ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １ Each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having nitrogen, oxygen, carbon, or halogen atoms bonded to the Si atom (provided that when X is a dialkylamino group, the total number of carbon atoms is 5 or more); a is an integer from 1 to 3; b is an integer from 0 to 2; and the sum of a and b is 1 to 3. ２ ｃ Si(H) ３－ｃ ) ３－ｄ NR ３ ｄ [2] (In the above general formula [2], R ２ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 5 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ３ Each is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ２ The total number of carbon atoms and R ３ The sum of the total number of carbon atoms is 5 or less, c is an integer from 1 to 3, and d is 0 or 1. (In the above general formula [3], R ４is a group independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, and R ５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Y is each independently -[(CR ６ ２ ) ｉ -Si(R ４ａ ) ２ -(provided that Si is bonded to N in the general formula [3]), or -[NR ５ａ -Si(R ４ａａ ) ２ ｊ -(provided that Si is bonded to N or C other than R ４ａａ , and N is bonded to Si or C other than R ５ａ ), and R ４ａ is a group independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, and R ４ａａ is a group independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, and R ５ａ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ６ is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 9 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, i is an integer from 0 to 9, j is an integer from 0 to 5, and h is an integer of i + 2×j + 1 (provided that 1≦h≦10).) 14. A vapor composition comprising at least one silicon compound selected from the group consisting of the gaseous following general formula [1], the following general formula [2], and the following general formula [3], and one or more gaseous aprotic solvents. R １ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １Each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having nitrogen, oxygen, carbon, or halogen atoms bonded to the Si atom (provided that when X is a dialkylamino group, the total number of carbon atoms is 5 or more); a is an integer from 1 to 3; b is an integer from 0 to 2; and the sum of a and b is 1 to 3. ２ ｃ Si(H) ３－ｃ ) ３－ｄ NR ３ ｄ [2] (In the above general formula [2], R ２ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 5 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ３ Each is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ２ The total number of carbon atoms and R ３ The sum of the total number of carbon atoms is 5 or less, c is an integer from 1 to 3, and d is 0 or 1. (In the above general formula [3], R ４ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Y is independently -[(CR ６ ２ ) ｉ -Si(R ４ａ ) ２ ]- (wherein Si is bonded to N in the general formula [3] above), or-[NR ５ａ -Si(R ４ａａ ) ２ ] ｊ - (However, Si is R ４ａａ It can also bond with N or C, and N is R ５ａ (Other than bonding with Si or C), R ４ａEach of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ４ａａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ａ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ６ ) is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 9 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, i is 0 to 9, j is 0 to 5, and h is an integer i + 2 × j + 1 (where 1 ≤ h ≤ 10). 15. A method for producing a vapor composition, comprising the step of subjecting a liquid surface treatment composition to at least a heat treatment to obtain a vapor composition obtained by vaporizing the liquid surface treatment composition, wherein the surface treatment composition comprises at least one silicon compound selected from the group consisting of the following general formulas [1], [2], and [3], and one or more aprotic solvents. R １ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １ Each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having nitrogen, oxygen, carbon, or halogen atoms bonded to the Si atom (provided that when X is a dialkylamino group, the total number of carbon atoms is 5 or more); a is an integer from 1 to 3; b is an integer from 0 to 2; and the sum of a and b is 1 to 3. ２ ｃ Si(H) ３－ｃ ) ３－ｄ NR ３ ｄ [2] (In the above general formula [2], R ２Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 5 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ３ Each is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ２ The total number of carbon atoms and R ３ The sum of the total number of carbon atoms is 5 or less, c is an integer from 1 to 3, and d is 0 or 1. (In the above general formula [3], R ４ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Y is independently -[(CR ６ ２ ) ｉ -Si(R ４ａ ) ２ ]- (wherein Si is bonded to N in the general formula [3] above), or-[NR ５ａ -Si(R ４ａａ ) ２ ] ｊ - (However, Si is R ４ａａ It can also bond with N or C, and N is R ５ａ (Other than bonding with Si or C), R ４ａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ４ａａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ａ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ６ This is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 9 carbon atoms, where some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, i is between 0 and 9, j is between 0 and 5, and h is an integer between i + 2 × j + 1 (where 1 ≤ h ≤ 10).

[0009] The present invention provides a vapor of a novel surface treatment composition and a method for manufacturing a wafer using the same.

[0010] This is a schematic perspective view of a wafer having a fine surface uneven pattern. This is a schematic cross-sectional view showing a portion of the a-a' section in Figure 1. This is a schematic cross-sectional view showing the state in which vapor of a surface treatment composition is supplied to a recess holding liquid. This is a schematic cross-sectional view of a wafer on which a water-repellent protective film has been formed.

[0011] Embodiments of the present invention will be described below with reference to the drawings. In all drawings, similar components are denoted by the same reference numerals, and their descriptions are omitted as appropriate. Also, the drawings are schematic diagrams and do not correspond to the actual dimensional ratios.

[0012] The following describes the surface treatment composition used in one embodiment of this disclosure.

[0013] The surface treatment composition used in this embodiment is supplied as vapor to the surface of a wafer having an uneven surface pattern and is used to form a water-repellent protective film on the surface. The surface treatment composition comprises at least one silicon compound selected from the group consisting of the following general formulas [1], [2], and [3], and one or more aprotic solvents.

[0014] In this specification, a "surface treatment composition" may exist in either a liquid state or a vapor state, at least in part or in whole. Hereinafter, the liquid before vaporization may be referred to as the "chemical solution" or "chemical solution of the surface treatment composition." Furthermore, hereafter, the vapor obtained by vaporizing this liquid may be referred to as "vapor," "vapor of the surface treatment composition," or "vapor composition."

[0015] By supplying the vapor of the surface treatment composition of this embodiment to the wafer surface, it is possible to form a water-repellent protective film on the wafer surface. Furthermore, by appropriately selecting the combination of the silicon compound contained in the surface treatment composition and the aprotic solvent, it is possible to form a protective film with excellent water repellency on the wafer surface. By applying the vapor of such a surface treatment composition to the manufacturing of wafers having an uneven surface pattern, it is possible to suppress the deformation of the uneven surface pattern.

[0016] Here, we will explain using semiconductor wafer manufacturing as an example. In the semiconductor wafer manufacturing process, fine uneven patterns are formed on the substrate (wafer) surface through processes such as film deposition, lithography, and etching. Subsequently, wet treatments such as cleaning using water or organic solvents are performed to clean the wafer surface, and a drying process is also carried out to remove any liquids such as cleaning solutions and rinsing solutions that adhere to the wafer during the wet treatment. It is known that during such drying processes, wafers with fine uneven patterns are prone to deformation and collapse of the uneven patterns. By forming a water-repellent protective film on the uneven patterns using the vapor of a surface treatment composition and modifying the wafer surface so that it exhibits water repellency, it becomes possible to suppress deformation and collapse of the uneven patterns during the drying process. This makes it possible to realize a wafer manufacturing method with excellent manufacturing stability.

[0017] According to the inventors' findings, it has been found that by using a vapor containing at least one silicon compound selected from the group consisting of the following general formulas [1], [2], and [3], a water-repellent protective film with water repellency equivalent to or better than that obtained when conventional surface treatment compositions containing HMDS or TMSMDMA are used as vapor can be formed on the wafer surface.

[0018] The composition of the surface treatment composition of this embodiment will be described in detail below.

[0019] (Silicon Compounds) The surface treatment composition contains at least one silicon compound selected from the group consisting of the following general formulas [1] to [3]. That is, the surface treatment composition in this disclosure contains any of the following: a silicon compound represented by the following general formula [1] only, a silicon compound represented by the following general formula [2] only, a silicon compound represented by the following general formula [3] only, a mixture of a silicon compound represented by the following general formula [1] and a silicon compound represented by the following general formula [2], a mixture of a silicon compound represented by the following general formula [1] and a silicon compound represented by the following general formula [3], a mixture of a silicon compound represented by the following general formula [2] and a silicon compound represented by the following general formula [3], or a mixture of a silicon compound represented by the following general formula [1], a silicon compound represented by the following general formula [2] and a silicon compound represented by the following general formula [3].

[0020] R １ ａ Si(H) ｂ X ４－ａ－ｂ [1] In the above general formula [1], R １ Each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms (provided that when X is a dialkylamino group, the total number of carbon atoms is 5 or more); a is an integer from 1 to 3, b is an integer from 0 to 2, and the sum of a and b is 1 to 3. Note that cyclic amino groups are not included in the dialkylamino group. If X contains a nitrogen atom bonded to a Si atom, that nitrogen atom is directly bonded to one Si atom.

[0021] (R ２ ｃ Si(H) ３－ｃ ) ３－ｄ NR ３ ｄ [2] In the above general formula [2], R ２Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 5 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ３ Each is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ２ The total number of carbon atoms and R ３ The sum of the total number of carbon atoms and the number of carbon atoms is 5 or less, c is an integer from 1 to 3, and d is 0 or 1. ２ The total number of carbon atoms and R ３ The sum of the total number of carbon atoms and the total number of carbon atoms shall be the value for the entire silicon compound shown in general formula [2].

[0022]

[0023] In the above general formula [3], R ４ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Y is independently -[(CR ６ ２ ) ｉ -Si(R ４ａ ) ２ ]- (wherein Si is bonded to N in the general formula [3] above), or-[NR ５ａ -Si(R ４ａａ ) ２ ] ｊ - (However, Si is R ４ａａ It can also bond with N or C, and N is R ５ａ (Other than bonding with Si or C), R ４ａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ４ａａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ａ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms.６ This is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 9 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, where i is from 0 to 9, j is from 0 to 5, and h is an integer of i + 2 × j + 1 (where 1 ≤ h ≤ 10).

[0024] Furthermore, R in the above general formula [1] １ , R in general formula [2] ２ , R in general formula [3] ４ , R ４ａ , R ４ａａ , R ６ R in the above general formula [1] may include unsaturated bonds, aromatic rings, and cyclic structures. １ , R in the above general formula [2] ２ , R in the above general formula [3] ４ , R ４ａ , R ４ａａ , R ６ As for each, independently, C ｅ H ２ｅ＋１ (e=1-10), C ｆ F ２ｆ＋１ CH ２ CH ２ (f = 1 to 8), and CF ｇ Cl ３－ｇ CH ２ CH ２ Examples include at least one monovalent hydrocarbon group selected from the group consisting of (g = 1 to 2). In addition, silicon compounds having monoalkylsilyl groups, silyldialkylsilyl groups, trialkylsilyl groups, etc., can be used as silicon compounds represented by general formula [1] or general formula [2]. Furthermore, from the viewpoint of further increasing water repellency, the R １ , R ４ , R ４ａ , R ４ａａ , R ６ Each of these is more preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms, even more preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, and even more preferably a monovalent hydrocarbon group having 1 carbon atom. Also, the R １ , R ４ , R ４ａ , R ４ａａ , R６ Each of them is more preferably a monovalent alkyl group having 1 to 6 carbon atoms, even more preferably a monovalent alkyl group having 1 to 4 carbon atoms, and even more preferably a monovalent alkyl group having 1 carbon atom. Furthermore, from the viewpoint of further increasing water repellency, the R ２ Each of these is more preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms, and even more preferably the hydrocarbon group has 1 carbon atom. ２ Each of them is more preferably a monovalent alkyl group having 1 to 4 carbon atoms, and even more preferably an alkyl group having 1 carbon atom. Also, the R １ , R ２ , R ４ , R ４ａ , R ４ａａ , R ６ The hydrogen atoms of the monovalent hydrocarbon group and alkyl group may be partially or entirely replaced by fluorine atoms or chlorine atoms, or partially or entirely replaced by fluorine atoms and / or chlorine atoms.

[0025] R in the above general formula [3] ５ , R ５ａ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ３ , R ５ , R ５ａ When is a monovalent hydrocarbon group, it is preferably one to six carbon atoms. Also, R in the above general formula [2] ３ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms. ３ When it is a monovalent hydrocarbon group, it is preferably one to four carbon atoms.

[0026] In the general formula [1] above, the monovalent group X, in which the atom bonded to the Si atom is nitrogen, oxygen, or carbon, may also include hydrogen atoms, carbon atoms, nitrogen atoms, oxygen atoms, silicon atoms, halogen atoms, and the like.

[0027] In the general formula [1] above, examples of monovalent nitrogen groups in X that bond to the Si atom include, for example, isocyanate groups, amino groups, dialkylamino groups with a total of 5 or more carbon atoms, isothiocyanate groups, azide groups, acetamide groups, and -NHC(=O)CF ３ , -NHC(=O)CF ２ Cl, -N(CH ３ )C(=O)CH ３ , -N(CH ３ ) C (= O) CF ３ , -N(CH ３ ) C (= O) CF ２ Cl, -N=C(CH ３ )OSi(CH ３ ) ３ -N=C(CF ３ )OSi(CH ３ ) ３ , -NHC(=O)-OSi(CH ３ ) ３ , -NHC(=O)-NH-Si(CH ３ ) ３ Pyrrolidine ring, imidazole ring, triazole ring, tetrazole ring, oxazolidinone ring, morpholine ring, -NH-C(=O)-Si(CH ３ ) ３ Furthermore, substituents that take the structure of the following general formula [1-2] -N(S(=O) ２ R ａ４ ) ２ [1-2] (Here, R ａ４ Each of these is independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and a fluorine atom. Also, substituents having the structure of the following general formula [1-3]. (In the above general formula [1-3], R ａ５ Each of these is independently a divalent hydrocarbon group having 1 to 8 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms. Also, substituents having the structure of the following general formulas [1-4] and [1-5] -N=C(NR ａ６ ２ ) ２[1-4] -N=C(NR ａ６ ２ ) R ａ６ [1-5] (In the above general formulas [1-4] and [1-5], R ａ６ These are, independently, a hydrogen group, a -C≡N group, and -NO. ２ A substituent is selected from a monovalent hydrocarbon group in which some or all of the hydrogen atoms are replaced with fluorine or chlorine atoms, and the hydrocarbon group may have oxygen and / or nitrogen atoms. Also, substituents having the structure of the following general formula [1-6] -N(R ａ７ )-C(=O)R ａ８ [1-6] (In the above general formula [1-6], the above R ａ７ R represents a hydrogen atom, a methyl group, a trimethylsilyl group, or a dimethylsilyl group. ａ８ Each of these independently represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms. ) and others.

[0028] Examples of silicon compounds in which X in the above general formula [1] is a monovalent group in which the atom bonded to the Si atom 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 (CH) ３ ) ２ Si(NH) ２ ) ２ C ２ H ５ Si(CH) ３ (NH ２ ) ２ (C) ２ H ５ ) ２ Si(NH) ２ ) ２ C ３ H ７ Si(CH) ３ (NH ２ ) ２ (C) ３ H ７ ) ２ Si(NH) ２ ) ２ C ４ H ９ Si(CH) ３ (NH ２ ) ２ (C) ４ H ９ ) ２ Si(NH) ２ ) ２ C ５ H １１ Si(CH) ３ (NH ２ ) ２ C ６ H １３ Si(CH) ３ (NH ２ ) ２ C ７ H １５ Si(CH) ３ (NH ２ ) ２ C ８ H １７ Si(CH) ３ (NH ２ ) ２ C ９ H １９Si(CH) ３ (NH ２ ) ２ C １０ H ２１ Si(CH) ３ (NH ２ ) ２ (CH) ３ ) ３ Sinh ２ C ２ H ５ Si(CH) ３ ) ２ NH ２ (C) ２ H ５ ) ２ Si(CH) ３ )NH ２ (C) ２ H ５ ) ３ Sinh ２ C ３ H ７ Si(CH) ３ ) ２ NH ２ (C) ３ H ７ ) ２ Si(CH) ３ )NH ２ (C) ３ H ７ ) ３ Sinh ２ C ４ H ９ Si(CH) ３ ) ２ NH ２ (C) ４ H ９ ) ３ Sinh ２ C ５ H １１ Si(CH) ３ ) ２ NH ２ C ６ H １３ Si(CH) ３ ) ２ NH ２ C ７ H １５ Si(CH) ３ ) ２ NH ２ C ８ H １７Si(CH) ３ ) ２ NH ２ C ９ H １９ Si(CH) ３ ) ２ NH ２ C １０ H ２１ Si(CH) ３ ) ２ NH ２ (CH) ３ ) ２ Si(H)NH ２ CH ３ Si(H) ２ NH ２ (C) ２ H ５ ) ２ Si(H)NH ２ C ２ H ５ Si(H) ２ NH ２ C ２ H ５ Si(CH) ３ )(H)NH ２ (C) ３ H ７ ) ２ Si(H)NH ２ C ３ H ７ Si(H) ２ NH ２ CF ３ CH ２ CH ２ Si(NH) ２ ) ３ C ２ F ５ CH ２ CH ２ Si(NH) ２ ) ３ C ３ F ７ CH ２ CH ２ Si(NH) ２ ) ３ C ４ F ９ CH ２ CH ２ Si(NH) ２ ) ３ C ５ F １１ CH２ CH ２ Si(NH) ２ ) ３ C ６ F １３ CH ２ CH ２ Si(NH) ２ ) ３ C ７ F １５ CH ２ CH ２ Si(NH) ２ ) ３ C ８ F １７ CH ２ CH ２ Si(NH) ２ ) ３ CF ３ CH ２ CH ２ Si(CH) ３ (NH ２ ) ２ C ２ F ５ CH ２ CH ２ Si(CH) ３ (NH ２ ) ２ C ３ F ７ CH ２ CH ２ Si(CH) ３ (NH ２ ) ２ C ４ F ９ CH ２ CH ２ Si(CH) ３ (NH ２ ) ２ C ５ F １１ CH ２ CH ２ Si(CH) ３ (NH ２ ) ２ C ６ F １３ CH ２ CH ２ Si(CH) ３ (NH ２ ) ２ C ７ F １５ CH２ CH ２ Si(CH) ３ (NH ２ ) ２ C ８ F １７ CH ２ CH ２ Si(CH) ３ (NH ２ ) ２ CF ３ CH ２ CH ２ Si(CH) ３ ) ２ NH ２ C ２ F ５ CH ２ CH ２ Si(CH) ３ ) ２ NH ２ C ３ F ７ CH ２ CH ２ Si(CH) ３ ) ２ NH ２ C ４ F ９ CH ２ CH ２ Si(CH) ３ ) ２ NH ２ C ５ F １１ CH ２ CH ２ Si(CH) ３ ) ２ NH ２ C ６ F １３ CH ２ CH ２ Si(CH) ３ ) ２ NH ２ C ７ F １５ CH ２ CH ２ Si(CH) ３ ) ２ NH ２ C ８ F １７ CH ２ CH ２ Si(CH) ３ ) ２NH ２ CF ３ CH ２ CH ２ Si(CH ３ ) (H)NH ２ CF ２ ClCH ２ CH ２ Si(CH ３ ) (NH ２ ) ２ CFCl ２ CH ２ CH ２ Si(CH ３ ) (NH ２ ) ２ CF ２ ClCH ２ CH ２ Si(CH ３ ) ２ NH ２ CFCl ２ CH ２ CH ２ Si(CH ３ ) ２ NH ２ CF ２ ClCH ２ CH ２ Si(CH ３ ) (H)NH ２ CFCl ２ CH ２ CH ２ Si(CH ３ ) (H)NH ２、 aminosilanes such as aminodimethylvinylsilane, aminodimethylphenylethylsilane, aminodimethylphenylsilane, aminomethyldiphenylsilane, aminodimethyl-t-butylsilane, or the amino group (-NH) of the aminosilane ２ The group can be -N=C=O, a dialkylamino group with a total of 5 or more carbon atoms, -N=C=S, or -N ３ , -NHC(=O)CH ３ , -NHC(=O)CF ３ , -NHC(=O)CF ２ Cl, -N(CH ３ )C(=O)CH ３ , -N(CH ３ ) C (= O) CF ３ , -N(CH３ ) C (= O) CF ２ Cl, -N=C(CH ３ )OSi(CH ３ ) ３ -N=C(CF ３ )OSi(CH ３ ) ３ , -NHC(=O)-OSi(CH ３ ) ３ , -NHC(=O)-NH-Si(CH ３ ) ３ (e.g., N,N'-bis(trimethylsilyl)urea), pyrrolidine ring (e.g., N-trimethylsilylpyrrolidine), imidazole ring (e.g., N-trimethylsilylimidazole), triazole ring (e.g., N-trimethylsilyltriazole), tetrazole ring, oxazolidinone ring, morpholine ring, -NH-C(=O)-Si(CH ３ ) ３ Furthermore, substituents that take the structure of the general formula [1-2] described above -N(S(=O) ２ R ａ４ ) ２ [1-2] (R ａ４ As described above, for example, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide, etc., and substituents that take the structure of the general formula [1-3] described above. (In the above general formula [1-3], R ａ５ As described above, for example, N-(trimethylsilyl)N,N-difluoromethane-1,3-bis(sulfonyl)imide, and substituents taking the structure of the general formulas [1-4] and [1-5] described above -N=C(NR ａ６ ２ ) ２ [1-4] -N=C(NR ａ６ ２ ) R ａ６ [1-5] (In the above general formulas [1-4] and [1-5], R ａ６ As described above, for example, 2-trimethylsilyl-1,1,3,3-tetramethylguanidine, and substituents that take the structure of the general formula [1-6] described above -N(R ａ７ )-C(=O)R ａ８　[1-6] (In the above general formula [1-6], R ａ７ , R ａ８ As described above, examples include N-trimethylsilylacetamide, N-trimethylsilyltrifluoroacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bis(trimethylsilyl)acetamide, bis(trimethylsilyl)trifluoroacetamide, etc., which are substitutions of the above.

[0029] In the above general formula [1], a silicon compound in which X is a monovalent group with an oxygen atom bonded to the Si atom is, for example, the amino group (-NH) of the above-mentioned aminosilane. ２ Base) to -O-C(=A)R ａ９ (Here, A is O, CHR) ａ１０ CHOR ａ１０ CR ａ１０ R ａ１０ , or NR ａ１１ R ａ９ , R ａ１０ Each of these independently represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a trialkylsilyl group, a trialkylsiloxy group, an alkoxy group, a phenyl group, a phenylethyl group, or an acetyl group, a group in which some or all of the hydrogen atoms of these groups are replaced with fluorine atoms and / or chlorine atoms, or a hydrogen atom, and the above 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 chlorodifluoroacetate, trimethylsilyl dichlorofluoroacetate, trimethylsilyl trichloroacetate, trimethylsilyl propionate, trimethylsilyl butyrate, etc. ), -O-C(R ａ１２ ) = N(R ａ１３ ) (Here, the above R ａ１２ R represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group, or a trialkylsilylamino group. ａ１３) -O-C(R ａ１４ )=CH-C(=O)R ａ１５ (Here, the above R ａ１４ and R ａ１５ Each of these independently represents a hydrogen atom or a monovalent organic group. For example, trimethylsilyloxy-3-penten-2-one, 2-trimethylsiloxypenta-2-en-4-one, etc., -OR ａ１６ (Here, the above R ａ１６ This represents saturated or unsaturated alkyl groups, saturated or unsaturated cycloalkyl groups, and fluorine-containing alkyl groups. For example, CH ３ Si(OCH) ３ ) ３ , C ２ H ５ Si(OCH) ３ ) ３ , C ３ H ７ Si(OCH) ３ ) ３ , C ４ H ９ Si(OCH) ３ ) ３ , C ５ H １１ Si(OCH) ３ ) ３ , C ６ H １３ Si(OCH) ３ ) ３ , C ７ H １５ Si(OCH) ３ ) ３ , C ８ H １７ Si(OCH) ３ ) ３ , C ９ H １９ Si(OCH) ３ ) ３ , C １０ H ２１ Si(OCH) ３ ) ３ , (CH ３ ) ２ Si(OCH) ３ ) ２ , C ２ H ５ Si(CH ３ ) (OCH３ ) ２ 、(C ２ H ５ ) ２ Si(OCH ３ ) ２ 、C ３ H ７ Si(H) ３ )(OCH ３ ) ２ 、(C ３ H ７ ) ２ Si(OCH ３ ) ２ 、C ４ H ９ Si(H) ３ )(OCH ３ ) ２ 、(C ４ H ９ ) ２ Si(OCH ３ ) ２ 、C ５ H １１ Si(H) ３ )(OCH ３ ) ２ 、C ６ H １３ Si(H) ３ )(OCH ３ ) ２ 、C ７ H １５ Si(H) ３ )(OCH ３ ) ２ 、C ８ H １７ Si(H) ３ )(OCH ３ ) ２ 、C ９ H １９ Si(H) ３ )(OCH ３ ) ２ 、C １０ H ２１ Si(H) ３ )(OCH ３ ) ２ ,(H ３ ) ３ SiOCH ３ 、C ２ H ５ Si(H) ３ ) ２ OCH３ 、(C ２ H ５ ) ２ Si(H) ３ )OCH ３ 、(C ２ H ５ ) ３ SiOCH ３ 、C ３ H ７ Si(H) ３ ) ２ OCH ３ 、(C ３ H ７ ) ２ Si(H) ３ )OCH ３ 、(C ３ H ７ ) ３ SiOCH ３ 、C ４ H ９ Si(H) ３ ) ２ OCH ３ 、(C ４ H ９ ) ３ SiOCH ３ 、C ５ H １１ Si(H) ３ ) ２ OCH ３ 、C ６ H １３ Si(H) ３ ) ２ OCH ３ 、C ７ H １５ Si(H) ３ ) ２ OCH ３ 、C ８ H １７ Si(H) ３ ) ２ OCH ３ 、C ９ H １９ Si(H) ３ ) ２ OCH ３ 、C １０ H ２１ Si(H) ３ ) ２ OCH ３ ,(H ３ ) ２Si(H)OCH ３ 、CH ３ Si(H) ２ OCH ３ 、(C ２ H ５ ) ２ Si(H)OCH ３ 、C ２ H ５ Si(H) ２ OCH ３ 、C ２ H ５ Si(CH ３ )(H)OCH ３ 、(C ３ H ７ ) ２ Si(H)OCH ３ 等 alkyl methoxysilanes, or, CF ３ CH ２ CH ２ Si(OCH ３ ) ３ 、C ２ F ５ CH ２ CH ２ Si(OCH ３ ) ３ 、C ３ F ７ CH ２ CH ２ Si(OCH ３ ) ３ 、C ４ F ９ CH ２ CH ２ Si(OCH ３ ) ３ 、C[[ID=X]] ５ F １１ CH ２ CH ２ [[ID=X]] ３ 、C ６ F １３ CH ２ CH ２ Si(OCH ３ ) ３ 、C ７ F １５ CH ２ CH ２ Si(OCH ３ ) ３ 、C ８ FIt should be noted that the original text seems to have some formatting or content issues that may require further clarification for a more accurate translation. For example, the repeated use of some tags and the presence of "X" in the middle which might be incorrect or incomplete information.​​１７ CH ２ CH ２ Si(OCH ３ ) ３ 、CF ３ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ２ F ５ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ３ F ７ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ４ F ９ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ５ F １１ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ６ F １３ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ７ F １５ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ８ F １７ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、CF ３ CH ２ CH ２ Si(H) ３ )２ OCH ３ 、C ２ F ５ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ３ F ７ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ４ F ９ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ５ F １１ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ６ F １３ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ７ F １５ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ８ F １７ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、CF ３ CH ２ CH ２ Si(H) ３ )(H)OCH ３、 CF ２ ClCH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、CFCl ２ CH ２ CH２ Si(CH) ３ ) (OCH ３ ) ２ CF ２ ClCH ２ CH ２ Si(CH) ３ ) ２ OCH ３ CFCl ２ CH ２ CH ２ Si(CH) ３ ) ２ OCH ３ CF ２ ClCH ２ CH ２ Si(CH) ３ ) (H) OCH ３ CFCl ２ CH ２ CH ２ Si(CH) ３ ) (H) OCH ３ Fluoroalkylmethoxysilanes and chlorofluoroalkylmethoxysilanes, or compounds in which the methyl group portion of the methoxy group of the above methoxysilane is replaced with a monovalent hydrocarbon group having 2 to 18 carbon atoms, some or all of which may be replaced with fluorine or chlorine atoms. ２ -R ａ１７ (Here, the above R ａ１７ These include alkyl groups with 1 to 6 carbon atoms, perfluoroalkyl groups, phenyl groups, tolyl groups, and -O-Si(CH ３ ) ３ The group is shown. For example, trimethylsilyl sulfonate, trimethylsilylbenzene sulfonate, trimethylsilyltoluene sulfonate, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl chlorodifluoromethanesulfonate, trimethylsilyl dichlorofluoromethanesulfonate, trimethylsilyl perfluorobutanesulfonate, bistrimethylsilyl sulfate, etc.), -O-P(-O-Si(CH ３ ) ３ ) ２ Examples include substitutions with (for example, tristrimethylsilyl phosphite).

[0030] Furthermore, specific examples of silicon compounds in which X in the above general formula [1] is a monovalent group in which the atom bonded to the Si atom is oxygen include hexamethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,1-triethyl-3,3-dimethyldisiloxane, 1,1,3,3-tetra-n-octyldimethyldisiloxane, bis(nonafluorohexyl)tetramethyldisiloxane, 1,3-bis(trifluoropropyl)tetramethyldisiloxane, and 1,3-di-n-butyltetramethyldisiloxane. Roxane, 1,3-di-n-octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, hexa-n-butyldisiloxane, hexaethyldisiloxane, hexavinyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, vinylpentamethyldisiloxane, 1,3-bis(3-chloroisobutyl)tetramethyldisiloxane, hexaphenyldisiloxane, 1,1,1-triethyl-3,3,3-trimethyldisiloxane, 1,3-bis(chloromethyl)tetramethyldisiloxane Til disiloxane, 1,1,3,3-tetraphenyldimethyldisiloxane, pentamethyldisiloxane, 1,3-bis(3-chloropropyl)tetramethyldisiloxane, 1,3-dichloro-1,3-diphenyl-1,3-dimethyldisiloxane, n-butyl-1,1,3,3-tetramethyldisiloxane, 1,3-di-t-butyldisiloxane, vinyl-1,1,3,3-tetramethyldisiloxane, 1,1,1-trimethyl-3,3,3-triphenyldisiloxane, 3,3-diphenyltetramethyltrisiloxane, 3-phenylheptame Tyltrisiloxane, 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-1,1,3,55-Pentamethyltrisiloxane, 1,3,5-Trivinyl-1,1,3,5,5-Pentamethyltrisiloxane, 1,3,5-Trivinyl-1,3,5-Trimethylcyclotrisiloxane, 3-Octylheptamethyltrisiloxane, 1,3,5-Triphenyltrimethylcyclotrisiloxane, 1,1,1,3,3,5,5-Heptamethyltrisiloxane, 1,1,3,3,5,5-Hexamethyltrisiloxane, 1,1,1,5,5,5-Hexaethyl-3-Methyltrisiloxane, Furfuryloxytrisiloxane, Tetrakis(dimethylsiloxy)silane, 1,1,3,3,5,5,7,7-Octamethyltetrasiloxane, Diphenyl Siloxane compounds such as siloxane-dimethylsiloxane copolymers, 1,3-diphenyl-1,3-dimethyldisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane, tetra-n-propyltetramethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, decamethyltetrasiloxane, dodecamethylcyclohexasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexaphenylcyclotrisiloxane, decamethylcyclopentasiloxane, and 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane are also examples.

[0031] In the above general formula [1], the silicon compound in which X is a monovalent group with an atom bonded to the Si atom being carbon is, for example, the amino group (-NH) of the above-mentioned aminosilane. ２ Base) to -C(S(=O) ２ R ７ ) ３ (Here, R ７ These are groups selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which some or all of the hydrogen atoms may be replaced with fluorine or chlorine atoms, and a fluorine atom. Examples include those substituted with (trimethylsilyl)tris(trifluoromethanesulfonyl)methide, etc.

[0032] Furthermore, as silicon compounds in which X in the above general formula [1] is a monovalent group whose atom bonded to the Si atom is a halogen, for example, the amino group (-NH) of the above-mentioned aminosilane. ２ Examples include those in which the group is replaced with a chloro group, bromo group, or iodine group (for example, chlorotrimethylsilane, bromotrimethylsilane, etc.).

[0033] Furthermore, the above general formula [1] is preferably N,O-bis(trimethylsilyl)acetamide, trimethylsilylimidazole, trimethylsilylmorpholine, or trimethylsilylpyrrolidine, and more preferably trimethylsilylimidazole.

[0034] Examples of silicon compounds represented by the above general formula [2] include 1,1,3,3-tetramethyldisilazane, bis(dimethylsilyl)methylamine, N,N-bis(methylsilyl)ethylamine, N-(dimethylsilyl)-1,1,1-trimethylsilanamine, and (silylamino)silylmethane. Preferably, 1,1,3,3-tetramethyldisilazane may be used.

[0035] Examples of silicon compounds represented by the above general formula [3] include cyclic disilazane compounds such as 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane and 2,2,6,6-tetramethyl-2,6-disila-1-azacyclohexane, cyclic trisilazane compounds such as 2,2,4,4,6,6-hexamethylcyclotrisilazane and 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane, and cyclic tetrasilazane compounds such as 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane. Preferably, 2,2,4,4,6,6-hexamethylcyclotrisilazane may be used.

[0036] Among the silicon compounds mentioned above, trimethylsilylamine, dimethylsilylamine, monomethylsilylamine, ethyldimethylsilylamine, propyldimethylsilylamine, butyldimethylsilylamine, hexyldimethylsilylamine, octyldimethylsilylamine, and decyldimethylsilylamine, with the amino group of the silylamine being -N=C=S, -N ３ , -NHC(=O)CH ３ , -N(CH ３ )C(=O)CH ３ -N=C(CH ３ )OSi(CH ３ ) ３ , -NHC(=O)-OSi(CH ３ ) ３ , -NHC(=O)-NH-Si(CH ３ ) ３ Pyrrolidine ring, imidazole ring, triazole ring, tetrazole ring, oxazolidinone ring, morpholine ring, -NH-C(=O)-Si(CH ３ ) ３ Substitutions such as 1,1,3,3-tetramethyldisilazane are preferred.

[0037] The silicon compound in this disclosure is preferably one having a trimethylsilyl group and a dimethylsilyl group, and more preferably one having a trimethylsilyl group. The silicon compound may also preferably be a silicon compound represented by general formula [1] or general formula [2], and more preferably the silicon compound may be a silicon compound represented by general formula [1].

[0038] It is preferable to use at least one silicon compound in this disclosure whose boiling point (PB1) at 1 atmosphere is 90 to 250°C. Using a silicon compound with a boiling point within the above range is preferable because it makes it easier to vaporize the chemical solution of the surface treatment composition and improves the water repellency of the wafer surface. More preferably, it may be 100 to 250°C, and even more preferably 130 to 250°C. In this specification, "~" indicates that the upper and lower limits are included unless otherwise specified. For example, when it is written as 90 to 250°C, it means 90°C or higher and 250°C or lower.

[0039] Examples of silicon compounds having a boiling point (PB1) of 90 to 250°C at 1 atmosphere include 1,1,3,3-tetramethyldisilazane, bis(dimethylsilyl)methylamine, N,N-bis(methylsilyl)ethylamine, N-(dimethylsilyl)-1,1,1-trimethylsilanamin, trimethylsilylpyrrolidine, bis(pyrrolidyl)dimethylsilane, trimethylsilyl isothiocyanate, trimethylsilylimidazole, ethyldimethylsilylimidazole, propyldimethylsilylimidazole, trimethylsilylmorpholine, N,O-bistrimethylsilylacetamide, bis(dimethylamino)diethylsilane, bis(diethylamino)dimethylsilane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, and 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane. Examples of silicon compounds having a boiling point (PB1) of 130 to 250°C at 1 atmosphere include trimethylsilylpyrrolidine, bis(pyrrolidyl)dimethylsilane, trimethylsilyl isothiocyanate, trimethylsilyl imidazole, ethyldimethylsilyl imidazole, propyldimethylsilyl imidazole, trimethylsilylmorpholine, N,O-bistrimethylsilylacetamide, bis(dimethylamino)diethylsilane, bis(diethylamino)dimethylsilane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, and 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane. Furthermore, from the viewpoint of further increasing water repellency, the boiling point (PB1) at 1 atmosphere is preferably 160 to 240°C. Examples of silicon compounds with a boiling point (PB1) of 160 to 240°C include trimethylsilyl imidazole, ethyldimethylsilyl imidazole, trimethylsilylmorpholine, N,O-bistrimethylsilylacetamide, bis(dimethylamino)diethylsilane, bis(diethylamino)dimethylsilane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, and 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane.

[0040] Furthermore, when the total silicon compounds contained in the surface treatment composition are considered as 100% by mass, it is preferable that the content of silicon compounds having a boiling point (PB1) of 90 to 250°C at 1 atmosphere be more than 50% by mass, more preferably 80% by mass or more, and even more preferably 98% by mass or more. If two or more silicon compounds are included in which PB1 falls within the above range, the total content of the two or more silicon compounds shall be referred to as the "content" above.

[0041] The lower limit of the silicon compound content in the surface treatment composition of the chemical solution is, for example, 0.3% by mass or more, preferably 1% by mass or more, and more preferably 2% by mass or more, when the surface treatment composition of the chemical solution is considered to be 100% by mass. This makes it easier for the surface treatment composition to improve water repellency. On the other hand, the upper limit of the silicon compound content in the chemical solution is, for example, 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, when the surface treatment composition of the chemical solution is considered to be 100% by mass. This improves storage stability. When two or more types of silicon compounds are present in the surface treatment composition, their total amount is considered the silicon compound content. Furthermore, the concentration of the vapor of the surface treatment composition obtained by vaporizing the entire chemical solution may be the same as the concentration of the chemical solution, as long as the entire amount is vaporized and remains in a state of not decomposing.

[0042] The surface treatment composition may contain any silicon atom-containing compound other than the silicon compound, as long as it does not significantly impair the performance of the wafer or water-repellent protective film obtained in this disclosure. The content of the arbitrary silicon atom-containing compound in the surface treatment composition is preferably less than the content of the silicon compound, preferably less than 0.3% by mass, and more preferably less than 0.1% by mass, when the surface treatment composition is 100% by mass.

[0043] (Aprotic Solvents) One or more aprotic solvents may be used as solvents for the surface treatment composition. The aprotic solvents described above refer to solvents that do not contain groups in which a hydrogen atom is bonded to an oxygen or nitrogen atom, such as hydroxyl groups or amino groups. The aprotic solvents used should be capable of dissolving the silicon compound.

[0044] An example of an aprotic solvent may include one or more selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen atom-containing solvents, sulfoxide solvents, carbonate solvents, polyhydric alcohol derivatives that do not have an OH group, nitrogen atom-containing solvents that do not have an N-H group, and silicone solvents. Among these, hydrocarbons, esters, ethers, halogen atom-containing solvents, sulfoxide solvents, and polyhydric alcohol derivatives that do not have an OH group are preferred.

[0045] Examples of the above 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-icosane, and branched hydrocarbons corresponding to the number of carbon atoms therein (e.g., isododecane, isocetane, etc.), cyclohexane, me Examples include chlorohexane, decalin, benzene, toluene, xylene, (ortho-, meta-, or para-)diethylbenzene, 1,3,5-trimethylbenzene, butylbenzene, naphthalene, p-menthane, o-menthane, m-menthane, diphenylmenthane, limonene, α-terpinene, β-terpinene, γ-terpinene, bornane, norbornane, pinan, α-pinene, β-pinene, karane, longifolene, and abietane.

[0046] Examples of the above esters include ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl n-octanoate, methyl decanoate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, dimethyl adipate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl ethoxyacetate.

[0047] In addition, cyclic esters such as lactone compounds may be used as the esters mentioned above. Examples of lactone compounds include β-propiolactone, γ-butyrolactone, γ-valerolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-nonanolactone, γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, and ε-hexanolactone.

[0048] Examples of the above ethers include di-n-propyl ether, ethyl-n-butyl ether, di-n-butyl ether, ethyl-n-amyl ether, di-n-amyl ether, ethyl-n-hexyl ether, di-n-hexyl ether, di-n-octyl ether, and ethers having branched hydrocarbon groups such as diisopropyl ether and diisoamyl ether, corresponding to the number of carbon atoms in these ethers, as well as dimethyl ether, diethyl ether, methyl ethyl ether, methylcyclopentyl ether, diphenyl ether, tetrahydrofuran, and dioxane.

[0049] Examples of the above ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, cyclohexanenone, and isophorone.

[0050] Examples of halogen atom-containing solvents include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, and hexafluorobenzene; hydrofluorocarbons such as 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, and Zeolora H (manufactured by Nippon Zeon Co., Ltd.); methyl perfluoropropyl ether, methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, methyl perfluorohexyl ether, ethyl perfluorohexyl ether; Asahiclean AE-3000 (manufactured by AGC Inc.); Novec HFE-7100; Novec Examples include hydrofluoroethers such as HFE-7200, Novec 7300, and Novec 7600 (all manufactured by 3M Japan Limited), chlorocarbons such as tetrachloromethane, hydrochlorocarbons such as chloroform, chlorofluorocarbons such as dichlorodifluoromethane, hydrochlorofluorocarbons such as 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, and 1,2-dichloro-3,3,3-trifluoropropene, as well as perfluoroethers and perfluoropolyethers.

[0051] Examples of the sulfoxide solvents mentioned above include dimethyl sulfoxide.

[0052] Examples of the carbonate-based solvents mentioned above include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate.

[0053] Examples of derivatives of the above polyhydric alcohols that do not have an OH group include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate Tate, 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,Examples include dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, glycerin triacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl propionate.

[0054] Examples of acyclic nitrogen atom-containing solvents that do not have the N-H group mentioned above include N,N-dimethylacetamide and triethylamine.

[0055] Examples of the silicone solvents mentioned above include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane.

[0056] From the viewpoint of cost and solubility, derivatives of polyhydric alcohols (however, those that do not have an OH group in the molecule) are preferred, for example, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol dimethyl ether, 3-methoxy-3-methyl-1-butyl acetate, and propylene glycol At least one selected from the group consisting of dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, and dipropylene glycol diacetate is preferred. Also preferred are propylene carbonate, linear or branched hydrocarbon solvents having 6 to 12 carbon atoms, p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, and pinan.

[0057] Among the above aprotic solvents, those that are polar (hereinafter sometimes referred to as aprotic polar solvents) may also be used. Examples of such aprotic polar solvents include derivatives of polyhydric alcohols that do not have an OH group, acyclic nitrogen atom-containing solvents represented by N,N-dimethylacetamide, lactone compounds represented by γ-butyrolactone, and sulfoxide-based solvents represented by dimethyl sulfoxide.

[0058] The aprotic solvent of this disclosure preferably contains one or more aprotic solvents A that satisfy the following condition A, as described later, and the total content of aprotic solvents A is 70% by mass or more of 100% by mass of the total amount of aprotic solvent. Condition A: When the boiling point (°C) of at least one of the silicon compounds at 1 atmosphere is PB1 and the boiling point (°C) of aprotic solvent A at 1 atmosphere is PB2, (PB1 - PB2) ≥ -10°C is satisfied.

[0059] According to the inventors' investigations, it was found that by using a vapor of a surface treatment composition obtained by combining the above-mentioned silicon compound and aprotic solvent A with an appropriate boiling point difference, the silicon compound in the vapor condenses more easily on the wafer surface, and the degree of concentration of the liquid silicon compound obtained by condensation can be relatively increased compared to the case where the above condition A is not met.

[0060] Although the detailed mechanism is not clear, it is thought that the vapor pressure of the silicon compound becomes lower than that of the solvent, causing it to preferentially condense on the wafer surface.

[0061] By using vapor with a high concentration of silicon compounds on the wafer surface, the above-mentioned water repellency can be further enhanced. Furthermore, when the concentration of silicon compounds in the liquid condensed on the wafer surface decreases, water repellency tends to decrease, and this tendency is particularly pronounced when silicon compound vapor is supplied to the wafer surface, as in this disclosure. Here, by using vapor with a high concentration of silicon compounds (i.e., vapor obtained from a chemical solution satisfying condition A), the degree of decrease in water repellency can be suppressed, eliminating the need to increase the concentration of silicon compounds in the chemical solution to obtain the desired water repellency. Moreover, even when using a chemical solution designed with a low silicon compound concentration, increasing the concentration can increase the concentration of silicon compounds in the liquid condensed on the wafer surface, allowing for efficient use of silicon compounds, which is preferable. Additionally, even for wafer surfaces with environmental conditions that easily decompose silicon compounds, such as wafer surfaces containing protic solvents, using vapor with a high concentration of silicon compounds can suppress the reduction in water repellency.

[0062] Furthermore, when the aprotic solvent is considered to be 100% by mass, the total content of the aprotic solvent A may preferably be 80 to 100% by mass, more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, even more preferably 98 to 100% by mass, and even more preferably 99.5 to 100% by mass.

[0063] The aprotic solvent A is preferably a solvent with a boiling point (PB2) of 90 to 240°C at 1 atmosphere. A boiling point within this range is preferable because it makes it easier to replace the cleaning solution with the aprotic solvent while maintaining a state where the wafer surface does not dry out when the vapor is supplied to the wafer surface. The upper limit of the boiling point may preferably be 200°C or less, 180°C or less, 150°C or less, 130°C or less, or 110°C or less. The lower limit of the boiling point may preferably be 100°C or higher.

[0064] Furthermore, the boiling point of the aprotic solvent that does not satisfy condition A is not particularly limited as long as it does not significantly hinder the formation of the water-repellent protective film or the pattern collapse prevention effect, but preferably the boiling point at 1 atmosphere is 90 to 240°C. More preferably it is 200°C or lower, 180°C or lower, 150°C or lower, 130°C or lower, or 110°C or lower. The lower limit of this boiling point is preferably 100°C or higher.

[0065] Furthermore, if two or more aprotic solvents are used in total and an azeotropic point is observed due to the coexistence of these solvents, the azeotropic point shall be treated as the boiling point. In addition, if the azeotropic point satisfies condition A, the azeotropic composition exhibiting the azeotropic point shall be designated as aprotic solvent A, and that azeotropic point shall be treated as the boiling point (PB2).

[0066] The solvent contained in the surface treatment composition of this disclosure is preferably substantially composed of aprotic solvents, but other solvents may be included as long as they do not impair the performance of the resulting water-repellent protective film. The term "aprotic solvent" as used herein refers to all aprotic solvents, including the aforementioned aprotic solvent A. Specifically, when the total solvent contained in the surface treatment composition is considered to be 100% by mass, it is preferable that 90% or more by mass is aprotic solvent, more preferably 95% or more by mass, even more preferably 98% or more by mass, and even more preferably 99.5% or more by mass. The above-mentioned "aprotic solvent" also includes aprotic polar solvents, and when there are two or more types of aprotic solvents, their total content is considered the aprotic solvent content.

[0067] (Surface treatment composition) As an example of the surface treatment composition used in this disclosure, the total content of the silicon compound and the aprotic solvent is preferably 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more, based on 100% by mass of the surface treatment composition. This makes it easier to improve water repellency.

[0068] Furthermore, the surface treatment composition preferably contains one or more aprotic solvents A that satisfy the following condition A, and the total content of the aprotic solvents A is 70% by mass or more of the total amount of the aprotic solvents 100% by mass. Condition A: When the boiling point (°C) of at least one of the silicon compounds at 1 atmosphere is PB1, and the boiling point (°C) of the aprotic solvent A at 1 atmosphere is PB2, then (PB1 - PB2) ≥ -10°C is satisfied. As described above, by setting the boiling point within the above range, when the vapor of the surface treatment composition changes state and becomes a liquid on the wafer surface, the concentration of the silicon compound contained in the liquid is increased, and the water repellency of the wafer surface is improved.

[0069] The lower limit of the boiling point difference between the silicon compound represented by (PB1-PB2) and the aprotic solvent A is preferably 0°C or higher, more preferably 1°C or higher, even more preferably 8°C or higher, even more preferably 20°C or higher, even more preferably 30°C or higher, even more preferably 40°C or higher, even more preferably 50°C or higher, and even more preferably 55°C or higher. The upper limit of the boiling point difference is preferably 160°C or lower, more preferably 140°C or lower, even more preferably 120°C or lower, and even more preferably 100°C or lower. It may also be preferable that the boiling point difference be between 0°C and 160°C.

[0070] When the surface treatment composition contains multiple types of silicon compounds, it is preferable that the boiling point difference between the boiling point (PB1) of at least one silicon compound at 1 atmosphere and the boiling point (PB2) of all aprotic solvents A at 1 atmosphere satisfies the aforementioned condition A. More preferably, when the total silicon compounds are 100% by mass, the content of silicon compounds that satisfy the above condition A may be more than 50% by mass, and even more preferably 98% by mass or more. Furthermore, when two or more silicon compounds satisfy the above condition A, that is, when the boiling point (PB1) of each silicon compound satisfies condition A, the total amount of silicon compounds that satisfy condition A is the aforementioned content.

[0071] The surface treatment composition preferably has a low water content, and is particularly preferably substantially water-free. "Substantially water-free" means that the amount of water does not affect the performance of the surface treatment composition; for example, it may be 1% by mass or less, preferably 0.3% by mass or less, of the surface treatment composition.

[0072] The surface treatment composition of this embodiment may contain other components besides those described above, as long as they do not hinder the objectives of the present invention. Examples of these other components include compounds containing silicon atoms other than the silicon compounds described above, solvents other than the aprotic solvents described above, surfactants, and antioxidants such as BHT (dibutylhydroxytoluene).

[0073] The above surface treatment composition may be catalyst-free or may be prepared to contain a catalyst in an amount of 5% by mass or less per 100% by mass of the surface treatment composition. The catalyst is a substance that promotes the reaction between the wafer surface and the silicon compound.

[0074] If a catalyst is not included, the surface treatment composition may be substantially free of catalysts. This is preferable because it makes it easier to improve the storage stability of the chemical solution. "Substantially free" means that it does not affect the performance of the surface treatment composition; for example, it may be less than 0.01% by mass in the surface treatment composition.

[0075] If a catalyst is included, the catalyst may be present in an amount of 0.01 to 5% by mass of 100% by mass of the surface treatment composition. If multiple catalysts are used, their total amount shall be 0.01 to 5% by mass.

[0076] Furthermore, it is preferable that the boiling point (PB3) of at least one catalyst at 1 atmosphere is equal to or greater than the boiling point (PB1) of the aprotic solvent at 1 atmosphere. By using such a catalyst, when the vapor changes state on the wafer surface and becomes a liquid, it is easier to increase the concentration of the catalyst contained in the liquid, thereby improving the reactivity between the wafer surface and the silicon compound. Moreover, it is even more preferable that the boiling point (PB3) of at least the catalyst is equal to or greater than the boiling point (PB2) of the aprotic solvent A. Furthermore, if the boiling point (PB3) of the catalyst is equal to or greater than the boiling point (PB1) of the silicon compound at 1 atmosphere, it is easier to improve the reactivity. That is, it is more preferable that PB3 ≥ PB1 ≥ PB2, and even more preferable that PB3 > PB1 > PB2.

[0077] Examples of catalysts include trimethylsilyl trifluoroacetate, trimethylsilyl chlorodifluoroacetate, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl chlorodifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl chlorodifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl chlorodifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl chlorodifluoromethanesulfonate Examples include nates, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl chlorodifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl chlorodifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, decyldimethylsilyl chlorodifluoroacetate, decyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl chlorodifluoromethanesulfonate, sulfonic acid, anhydride of the sulfonic acid, salt of the sulfonic acid, sulfonic acid derivatives, sulfonic acid esters, sulfonimides, sulfonimide derivatives, sulfonmethides, sulfonmethide derivatives, acid imides, nitrogen-containing heterocyclic compounds, and silylated heterocyclic compounds other than the silicon compounds.

[0078] The chemical solution of the surface treatment composition in this embodiment is obtained by mixing the above-mentioned components. Alternatively, it may be obtained by mixing the above-mentioned components and dissolving them. The resulting mixture or solution may be purified using an adsorbent or filter as needed. Alternatively, each component may be purified beforehand by distillation, or purified using an adsorbent or filter.

[0079] (Surface treatment composition for heating and vaporization) One preferred embodiment of the present disclosure is a surface treatment composition for heating and vaporization used to supply in vapor form to the surface of a wafer holding a cleaning solution, wherein the surface treatment composition comprises at least one silicon compound selected from the group consisting of general formula [1], general formula [2], and general formula [3], and one or more aprotic solvents.

[0080] The surface treatment composition for heating and vaporization in this embodiment refers to a surface treatment composition used for heating and vaporization in a device such as a vaporization chamber. Preferably, the surface treatment composition for heating and vaporization may be a surface treatment composition in liquid form. As mentioned above, when the term "surface treatment composition" is used in this specification, it means that at least part or all of it can exist in either a liquid state or a vapor state, while when it is explicitly stated as "surface treatment composition for heating and vaporization," the embodiment does not include the state in which the entire composition exists as a vapor. Furthermore, specific embodiments of the composition of the "surface treatment composition for heating and vaporization" shall be in accordance with the description in the (surface treatment composition) section mentioned above.

[0081] In this specification, "heat evaporation" refers to the evaporation of the chemical solution by heating within the apparatus, and the resulting gas (vapor) diffusing into the space within the apparatus. Furthermore, the above-mentioned "heat evaporation" can be carried out by known means as long as evaporation and diffusion occur through heating treatment under predetermined environmental conditions, and the heating temperature and pressure can be appropriately selected within a controllable range.

[0082] (Vapor Composition) Another preferred embodiment of the present disclosure is a vapor composition comprising at least one silicon compound selected from the group consisting of the above general formulas [1], [2], and [3] in gaseous form, and one or more gaseous aprotic solvents. Furthermore, specific embodiments of the "vapor composition," such as the components and component ratios, shall be in accordance with the description in the above section (Surface Treatment Composition), and the following will only describe matters not described in the above section (Surface Treatment Composition).

[0083] The vapor composition of this embodiment may contain the gaseous silicon compound and the gaseous aprotic solvent. Depending on the temperature and pressure, a portion of the vapor composition may liquefy in the space and become fine mist (droplets), but as long as the entire vapor composition does not become mist, it shall be treated as a vapor composition even if it contains mist. The term "mist" above refers to fine droplets that can float or flow in the space of the apparatus, and does not include droplets that adhere to the walls of the apparatus or wafers.

[0084] Furthermore, it is preferable that the vapor composition of this embodiment uses vapor obtained by vaporizing the chemical solution of the surface treatment composition. Alternatively, the silicon compound gas and the aprotic solvent gas may be prepared separately, and then these gases may be mixed to form the vapor composition. When the chemical solution is vaporized, the composition of the vapor composition described herein may be considered to be the same as the composition of the chemical solution before vaporization, provided that the entire volume is vaporized and no decomposition occurs. Furthermore, it is preferable that the temperature of the vapor composition be above the boiling point of the component of the vapor composition that exhibits the highest boiling point at a predetermined pressure, and below the decomposition temperature of all components of the vapor composition, as this allows for the formation of a stable gas.

[0085] The water repellency of the water-repellent protective film formed on the surface treatment composition can be evaluated using the water contact angle measured by the following procedure. The water contact angle of the silicon wafer surface after surface treatment may be, for example, 65° or more, 68° or more, preferably 80° or more, more preferably 81° or more, even more preferably 83° or more, even more preferably 85° or more, and even more preferably 90° or more. The larger the water contact angle, the higher the water repellency of the surface, and consequently, the surface can be said to have an excellent pattern deformation prevention effect. (Procedure) A smooth silicon wafer with a thermal oxide film (a Si wafer having a thermal oxide film layer with a thickness of 1 μm on the surface) is immersed in a 1% by mass aqueous hydrofluoric acid solution at 25°C for 10 minutes, then immersed in pure water at 25°C for 1 minute, and subsequently immersed in 2-propanol (hereinafter referred to as "iPA") at 25°C for 1 minute to prepare an evaluation silicon wafer (with iPA attached). Next, a total of 1 ml of the surface treatment composition solution is supplied to the heated vaporization chamber, and the entire amount of the solution is vaporized. The heating temperature of the vaporization chamber is set below the temperature at which the entire amount of the solution is vaporized and the individual components contained in the solution do not undergo thermal decomposition. Next, 2 dm³ of nitrogen gas is supplied to the vaporization chamber. ３ The steam is moved from the vaporization chamber to the steam treatment chamber at a flow rate of one minute. Furthermore, the silicon wafer with IPA attached is placed in the steam treatment chamber for 60 seconds with the surface to be treated horizontal and facing downwards, and tilted at 45° from the horizontal (the angle between the normal vector of the surface to be treated on the wafer and the vertical vector is 135°). A portion of the steam is condensed on the surface of the silicon wafer, replacing the IPA. After that, the silicon wafer is removed from the steam treatment chamber and immersed in iPA at 25°C for 1 minute. Finally, the silicon wafer is removed from the iPA and air is blown on to remove the iPA from the surface. With the silicon wafer obtained through the above process placed horizontally on the treated surface, 2 μl of pure water is placed on top of it, and the angle between the water droplet and the treated surface (water contact angle) is measured using a contact angle meter (Kyowa Interface Science Co., Ltd.: CA-X type) in accordance with JIS R 3257:1999 "Test method for wettability of substrate glass surface".

[0086] In the chemical solution of the surface treatment composition, the number of particles larger than 0.2 μm, as measured using a light scattering type liquid particle detector, is, for example, 1.0 × 10¹⁶ per 1 mL of the surface treatment composition. ４ Less than or equal to 1.0 × 10 ３ Less than or equal to 1.0 × 10 ２ The number may be less than or equal to 0.2 μm. This suppresses the risk of contamination of the vapor processing equipment, the vaporization chamber that vaporizes the surface treatment composition, and other liquid supply sections, which could lead to a decrease in device yield and reliability. While fewer particles larger than 0.2 μm are preferable, there may be one or more particles per 1 mL of the composition as long as they are within the above content range. Particle measurement of the chemical solution in the surface treatment composition is performed using a commercially available measuring device that employs a light scattering type liquid particle measurement method with a laser as the light source, and the particle size refers to the light scattering equivalent diameter based on PSL (polystyrene latex) standard particles. Particles include dust, dirt, organic solids, inorganic solids, etc., that are included as impurities in the materials of each component of the surface treatment composition, and dust, dirt, organic solids, inorganic solids, etc., that are introduced as contaminants during the preparation of the composition, and which ultimately remain as particles in the composition without dissolving.

[0087] In the chemical solution of the surface treatment composition, the total content of Na, Mg, Ca, Mn, Fe, Cu, Li, Al, Cr, Ni, Zn, and Ag, as measured by inductively coupled plasma mass spectrometry, may be, for example, 100 ppb by mass or less, preferably 10 ppb by mass or less, and more preferably 1 ppb by mass or less. This suppresses the risk of contamination inside the steam treatment device, which could lead to a decrease in device yield and reliability. While a lower total content is preferable, within the above range, the content of each element may be 0.0001 ppb by mass or more relative to the total amount of the composition.

[0088] (Wafer manufacturing method) The following describes a wafer manufacturing method using a surface treatment composition.

[0089] The wafer manufacturing method of this embodiment includes the steps of: preparing a wafer having an uneven pattern on its surface (preparation step); supplying a cleaning solution to the surface of the wafer and cleaning it (cleaning step); and supplying vapor of the surface treatment composition to the surface holding the cleaning solution, changing the state of the vapor to a liquid on the surface, replacing the cleaning solution with the liquid, and forming a water-repellent protective film on at least a part of the surface (surface treatment step). In addition to the above steps, one or more steps such as a pre-rinse (first rinse), a post-rinse (second rinse), a cleaning step, a drying step, and a water-repellent protective film removal step may be performed. The surface treatment composition used in the wafer manufacturing method of this embodiment can be the same as the surface treatment composition described above.

[0090] Figures 1 to 4 show an example of a wafer manufacturing process using a surface treatment composition (hereinafter sometimes simply referred to as "composition"). Figure 1 is a schematic perspective view of a wafer 1 whose surface has a fine uneven pattern 2. Figure 2 is a schematic cross-sectional view of the wafer 1 showing a part of the a-a' section in Figure 1. Figure 3 shows the process of supplying vapor 9 of the composition to a recess 4 holding liquid 8. Figure 4 shows the process of forming a water-repellent protective film 11 with liquid 10 obtained by a state change (liquefaction) of the vapor of the composition.

[0091] (Preparation process) First, a wafer 1 having an uneven surface pattern is prepared.

[0092] In the preparation step for wafer 1, the following method, which is an example of a method for forming a textured pattern 2 on the wafer surface, may be used. First, a resist is applied to the wafer surface, then the resist is exposed through a resist mask, and the exposed or unexposed resist is removed to produce a resist having the desired textured pattern. Alternatively, a resist having a textured pattern can be obtained by pressing a mold with a pattern onto the resist. Next, the wafer is etched. At this time, the substrate surface corresponding to the recessed parts of the resist pattern is selectively etched. Finally, when the resist is peeled off, a wafer 1 having a textured pattern 2 on its surface is obtained.

[0093] The wafer on which the uneven pattern 2 is formed, and the material of the uneven pattern 2, are not particularly limited. Various wafers can be used as the material of wafer 1, such as silicon wafers, silicon carbide wafers, wafers composed of multiple components including silicon atoms, sapphire wafers, and various compound semiconductor wafers.

[0094] The material for the uneven pattern 2 may include one or more selected materials from the group consisting of Si, Ti, Ge, W, and Ru, or oxides, nitrides, nitrogen oxides, nitrided carbides, and oxides, including one or more of these. For example, the material for the uneven pattern 2 can be 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; materials combining these; and photoresist materials. Among these, materials containing Si are preferred, and silicon oxide is particularly preferred.

[0095] The uneven pattern 2 may consist of, for example, a three-dimensional structure having one or more structures arranged along the vertical direction of the surface, and / or one or more structures arranged along the horizontal direction perpendicular to the vertical direction. An example of such a three-dimensional structure may constitute at least part of a logic device or memory device, and examples include FinFETs, nanowire FETs, nanosheet FETs, other multi-gate type FETs, three-dimensional memory cells, etc.

[0096] Figure 2 is a cross-sectional view showing an example of a surface texture pattern 2. In this embodiment, the pattern dimensions of the surface texture pattern 2 can be defined as at least one width dimension in the in-plane direction of the surface, and / or at least one height dimension perpendicular to the surface. In the cross-sectional structure of the surface texture pattern 2 (in the substrate thickness direction), at least one pattern dimension of its width and height, or in the three-dimensional structure of the surface texture pattern 2 (three-dimensional coordinates of XYZ), at least one pattern dimension of its width (length in the X-axis direction), height (length in the Y-axis direction), and depth (length in the Z-axis direction) may be, for example, 30 nm or less, 20 nm or less, or 10 nm or less. This may also be the spacing between patterns. The surface treatment composition of this disclosure can be applied even when using a wafer 1 having such a fine surface texture pattern 2.

[0097] Such surface treatment compositions are suitable for use, for example, in surface treatment of a wafer 1 having an uneven pattern 2 with a pattern dimension of 30 nm or less, preferably 20 nm or less.

[0098] The aspect ratio of the protrusion 3 may be, for example, 3 or more, 5 or more, or 10 or more. Pattern collapse can be suppressed even in a recessed pattern 2 having a fragile structure of protrusion 3. On the other hand, the aspect ratio of the protrusion 3 is not particularly limited, but may be 100 or less. The aspect ratio of the protrusion 3 is expressed as the value obtained by dividing the height 6 of the protrusion by the width 7 of the protrusion.

[0099] Furthermore, the width 5 of the recess may be, for example, 70 nm or less, preferably 45 nm or less. The width 5 of the recess is indicated by the distance between adjacent protrusions 3 in the cross-sectional view of Figure 2.

[0100] (Cleaning step) Next, the surface of wafer 1 is cleaned with a cleaning solution (cleaning step). In the cleaning step, the surface of wafer 1 may be brought into contact with an aqueous cleaning solution, which is one of the cleaning solutions. Examples of aqueous cleaning solutions include water, alcohol, aqueous solution of ammonium hydroxide, aqueous solution of tetramethylammonium, aqueous solution of hydrofluoric acid, aqueous solution of hydrochloric acid, aqueous solution of hydrogen peroxide, aqueous solution of sulfuric acid, and other protic solvents, as well as organic solvents other than protic solvents (for example, the aprotic solvents mentioned above). These may be used individually or in combination of two or more.

[0101] The cleaning process may be performed once or more times before the surface treatment process or before the first rinsing process described later. Other processes may be included between multiple cleaning processes, or between the cleaning process and the surface treatment process.

[0102] (First rinsing step) Next, if necessary, it is preferable to bring the surface of the wafer 1 into contact with a first rinsing solution, which is one of the cleaning solutions (first rinsing step).

[0103] As the first rinse solution, a different cleaning solution from the aqueous cleaning solution used in the cleaning step can be used. Examples include water, organic solvents, mixtures thereof, or mixtures thereof with at least one of the following: acid, alkali, surfactant, or oxidizing agent. Examples of organic solvents used in the first rinse solution include hydrocarbons, esters, ethers, ketones, halogen atom-containing solvents, sulfoxide solvents, alcohols, derivatives of polyhydric alcohols, and nitrogen atom-containing solvents. Among these, it is preferable to use at least one protic solvent selected from alcohols with three or fewer carbon atoms, such as methanol, 1-propanol, and 2-propanol (isopropanol), as the organic solvent.

[0104] Furthermore, multiple types of first rinsing solutions may be used. For example, rinsing can be performed in the order of an acidic aqueous solution or an alkaline aqueous solution, followed by an organic solvent. Alternatively, an aqueous cleaning solution may be added, and rinsing can be performed in the order of an acidic aqueous solution or an alkaline aqueous solution, followed by the aqueous cleaning solution, and then an organic solvent.

[0105] The first rinsing step may be performed once or more times after the washing step or before the surface treatment step. Other steps may be included between multiple first rinsing steps, or between the first rinsing step and the surface treatment step.

[0106] The method for supplying the cleaning solution can be any known method, but examples include a single-wafer method, which is represented by a spin cleaning device that holds the wafer almost horizontally and rotates it while supplying the cleaning solution near the center of rotation to clean each wafer one by one, and a batch method, which uses a cleaning device that immerses and cleans multiple wafers in a cleaning tank. Alternatively, the cleaning solution may be supplied by steam, as in the surface treatment composition described later. This allows the cleaning solution to be retained in at least the recesses 4 of the uneven pattern 2 of the wafer 1.

[0107] (Surface treatment process) Next, with cleaning liquid (liquid 8) held in at least the recesses 4 of the uneven pattern 2, vapor 9 of the surface treatment composition of this embodiment is supplied to the surface of the uneven pattern, the vapor 9 is changed to liquid 10 on the wafer surface, and the liquid 8 held in at least the recesses 4 is replaced and held by the liquid 10, thereby forming a water-repellent protective film 11 (hereinafter sometimes referred to as "protective film 11") on at least a part of the wafer surface, for example, on the surface of the recesses 4.

[0108] When the vapor 9 of the surface treatment composition is supplied, the cleaning solution (liquid 8) held on the wafer surface may be the aqueous cleaning solution described above or the first rinse solution. From the viewpoint of manufacturing stability, the first rinse solution is preferred, and among these, a protic solvent such as 2-propanol (iPA) may be included. That is, in one embodiment of the wafer manufacturing method, the vapor 9 of the surface treatment composition may be supplied while iPA is held on the surface of the wafer.

[0109] Furthermore, when supplying the steam 9, the wafer surface (the surface to be processed) is preferably positioned with the wafer tilted from the horizontal, or with the surface to be processed facing downwards horizontally. This makes it easier to impart fluidity to the liquid held on the surface, even when the wafer 1 is stationary, and facilitates the exchange between the liquid 8 held on the wafer surface and the liquid 10 liquefied by the steam. The wafer orientation may also be as described above during cleaning processes and other processes other than the surface treatment process. More preferably, in the process of forming the water-repellent protective film, the angle between the normal vector of the wafer surface and the vertical vector may be greater than 0° and less than or equal to 180°. Note that if the two vectors are in the same direction and parallel, the angle between the two vectors is 0°. Also, the direction of the normal vector of the surface of a horizontally held wafer may be considered to coincide with the direction of the vertical vector. Specifically, when the angle is 0°, the wafer may be positioned so that the surface to be processed is horizontal and facing upwards, and when the angle is 180°, the wafer may be positioned so that the surface to be processed is horizontal and facing downwards.

[0110] One method for supplying the vapor 9 of the surface treatment composition is to place a wafer 1, which holds liquid 8 in at least the recesses 4 of the uneven pattern 2, in a vapor treatment chamber (hereinafter sometimes referred to as a "chamber"), and separately, to supply a vapor composition (vapor 9) obtained by heating and vaporizing a surface treatment composition for heating and vaporization in a vaporization section such as a vaporization chamber, to the uneven pattern surface via piping or nozzles. A carrier gas such as nitrogen gas or dry air may be used when supplying the vapor composition. In addition, the vapor composition after being transferred from the vaporization section may be diluted by the carrier gas, and the composition of the mixed gas containing the vapor composition and the carrier gas may not necessarily match that of the vapor composition. In this specification, the vapor composition is referred to as vapor 9, and for convenience, it is stated that vapor 9 was supplied to the wafer surface, but as mentioned above, a mixed gas containing a carrier gas may also be supplied. It should be noted that it is the vapor composition (vapor 9) that changes state on the wafer surface, and the carrier gas does not liquefy.

[0111] As described above, the method of using the surface treatment composition may include a step of supplying the surface treatment composition in vapor form to the surface of a wafer holding a cleaning solution. Furthermore, in the method of use, the supply of the surface treatment composition vapor may be carried out together with the carrier gas described above.

[0112] The method for vaporizing the surface treatment composition is not particularly limited to the method described above. For example, a batch-type vaporization method is used in which a predetermined amount of a surface treatment composition liquid for heating and vaporization is introduced into a vaporization chamber, sufficient heating is performed to evaporate the entire surface treatment composition, and after complete evaporation, the vaporized composition (vapor 9) is sent to pipes or nozzles to be supplied to the surface of the uneven pattern.

[0113] Another example is a continuous vaporization method in which droplets of a surface treatment composition for heating and vaporization are dropped onto a small, preheated vaporization section (for example, by providing a heating means in a part of the piping), and the entire amount of the surface treatment composition droplets is evaporated each time they are dropped, and the vapor composition (vapor 9) is sent to pipes or nozzles to be supplied to the surface of the uneven pattern. In addition to the above, for example, a gaseous silicon compound and a gaseous aprotic solvent may be prepared separately and sent to the chamber, vaporization chamber, vaporization section, etc., to obtain the desired composition. A carrier gas or diluent gas may also be used at this time.

[0114] The vaporization temperature should be above the temperature at which the component with the highest boiling point in the surface treatment composition for heating and evaporation vaporizes, but it is preferable to keep the temperature low so as not to cause thermal decomposition of the silicon compound, which is a protective film-forming component, or thermal decomposition of the aprotic solvent. Preferred conditions for supplying the steam 9 include introducing nitrogen gas as described above, and supplying the mixed gas to the surface of the uneven pattern after the composition of the steam composition obtained as described above and the nitrogen gas has become constant.

[0115] Figure 3 shows a schematic diagram of the state in which vapor 9 is supplied to a recess 4 that holds liquid 8. Figure 4 shows a schematic diagram of the state in the recess 4 in which a water-repellent protective film 11 is formed by the liquid 10 obtained by the vapor 9 of the surface treatment composition undergoing a state change. The wafer 1 in the schematic diagrams of Figures 3 and 4 shows a part of the a-a' cross section of Figure 1.

[0116] As shown in Figures 3 and 4, the supplied vapor 9 changes state to liquid 10 in the recess 4, the liquid 10 replaces the liquid 8 held in the recess 4, and the liquid 10 is held in the recess 4. In addition, temperature adjustments such as lowering or keeping the temperature of the wafer 1 and recess 4 constant may be made in order to promote or stabilize the above state change. Furthermore, in order to prevent the wafer surface from drying out due to volatilization before the liquid 8 held in the recess 4 is replaced by liquid 10, it is preferable to maintain the temperature of the wafer 1 at a temperature lower than the boiling point of the liquid 8 held in the recess 4. The composition of liquid 10 may be the same as or different from the composition of vapor 9, and may or may not change over time, but at least a portion of the silicon compounds contained in vapor 9 will always liquefy and be included in liquid 10 within the processing time of the surface treatment process.

[0117] One preferred embodiment of the present disclosure involves heating and evaporating a surface treatment composition for heating and evaporation containing the aprotic solvent A, and supplying the resulting vapor composition as vapor 9 to the wafer surface, thereby liquefying the vapor 9 into liquid 10. Compared to vapor compositions that do not satisfy condition A, such vapor compositions tend to show preferential condensation of silicon compounds, making it easier to increase the silicon compound content in the liquid 10. In the examples described later, it was found that the liquid 10 obtained in this way easily increases the water contact angle on the wafer surface.

[0118] On the wafer surface, the silicon compound of liquid 10 reacts with the wafer surface, and the portion having the water-repellent functional group described above is fixed to the wafer surface, thereby forming a water-repellent protective film 11 (protective film 11).

[0119] The protective film 11 does not necessarily have to be formed continuously or uniformly, but it is more preferable that it be formed continuously and uniformly in order to provide better water repellency.

[0120] By replacing the liquid 8 held on the wafer surface, such as the first rinse solution or aqueous cleaning solution, with the liquid 10 obtained by liquefying the vapor 9 of the surface treatment composition, it becomes possible to perform surface modification treatment, i.e., form a protective film 11, before the surface of the uneven pattern 2 on the wafer 1 dries. This suppresses the collapse of the uneven pattern 2.

[0121] If it does not cause pattern deformation or significantly impair the performance of the protective film, known methods such as heating, reduced pressure, and drying may be applied to the liquid 10 held on the wafer surface to promote the formation of the protective film 11, as needed.

[0122] (Second rinsing step) Next, if necessary, the wafer surface on which the protective film 11 is formed may be brought into contact with a second rinsing solution (second rinsing step). As the second rinsing solution, the one exemplified in the first rinsing solution can be used.

[0123] Furthermore, multiple types of second rinsing solutions may be used. For example, rinsing can be performed by contacting solvents such as water and isopropanol in that order.

[0124] The second rinsing step may be performed once or more times after the surface treatment step. Other steps may be included between multiple second rinsing steps, and between the surface treatment step and the second rinsing step.

[0125] (Drying process) After the formation of the protective film 11, a drying process may be performed to dry the surface of the wafer 1 as needed. The drying process can remove any residual liquid present on the surface of the wafer 1. The residual liquid may include liquid 10, a second rinse solution, or a mixture thereof. As drying means, known methods such as spin drying, iPA (2-propanol) vapor drying, Marangoni drying, heating drying, hot air drying, vacuum drying, and reduced pressure drying may be used.

[0126] The drying process may be performed once or more times, for example, after the surface treatment process or after the second rinsing process. The drying process and the second rinsing process may be repeated alternately.

[0127] (Removal step) Next, the protective film 11 on the surface of the wafer 1 may be removed (removal step). Removal means include heating, UV irradiation, ozone exposure, plasma irradiation, corona discharge, etc. Treatment with a concentrated fluid such as a supercritical fluid (which may contain acids, bases, and oxidizing agents), or steam treatment may also be performed. These may be used individually or in combination of two or more. These treatments may be performed under atmospheric pressure or under reduced pressure.

[0128] As a result, a wafer 1 (semiconductor substrate) using the surface treatment composition of this embodiment can be obtained.

[0129] The manufacturing methods shown in Figures 1 to 4 are for wafer patterns, but the present invention is not limited thereto. The substrate manufacturing method of this embodiment can also be applied to resist patterns, and the deformation of the resist pattern can be suppressed by using the surface treatment composition of the present invention in the cleaning and drying process.

[0130] The above supply process describes a manufacturing method performed after the cleaning process, but is not limited to this, and may be performed after various treatments applied to the uneven pattern 2. In addition to the above process, the substrate manufacturing method may also use one or more known treatments in combination. For example, a surface treatment such as plasma treatment may be performed after the above removal process.

[0131] (Cleaning process) After manufacturing wafer 1 and removing it from the apparatus, a further cleaning process of the apparatus may be performed. It is also preferable to include a cleaning process of the chamber in which the surface treatment process was performed. The cleaning method can be any known method, for example, supplying a cleaning liquid into the apparatus by running water, spraying, etc., or supplying it by steam in the same way as the surface treatment composition.

[0132] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., within the scope that can achieve the objectives of the present invention are included in the present invention.

[0133] The following are examples that more specifically disclose embodiments of the present invention. However, the present invention is not limited to these embodiments.

[0134] [Example 1] (Preparation of the chemical solution for the surface treatment composition) 5 g of N,O-bis(trimethylsilyl)acetamide (chemical formula (I) below, hereinafter abbreviated as "BSA") as a silicon compound and 95 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA") as an aprotic solvent were mixed to obtain a surface treatment composition (hereinafter abbreviated as "composition"). This preparation was carried out by N ２ The procedure was carried out in a glove box under controlled conditions. PGMEA and BSA were placed in a container in that order and mixed to obtain a surface treatment composition (chemical solution).

[0135] The concentration of silicon compounds in the prepared composition was evaluated when the chemical solution was vaporized and condensed on the wafer surface as described below, and the results are shown in Table 1. The water repellency of the wafer surface after surface treatment (water contact angle of the water-repellent protective film formed on the wafer surface) was also evaluated and is shown in Table 1.

[0136] [Examples 2 to 10, and Comparative Examples 1 to 5] The chemical solutions of the compositions were prepared in the same manner as in Example 1, except that the types and contents of each component were as shown in Table 1, and various evaluations were performed. The results are shown in Table 1. [Examples 11 to 13] The chemical solutions of the compositions were prepared in the same manner as in Example 1, except that the types and contents of each component were as shown in Table 2, and the water repellency of the wafer surface after surface treatment (water contact angle of the water-repellent protective film formed on the wafer surface) was evaluated and is also shown in Table 2.

[0137] The compound names corresponding to the abbreviations listed in Tables 1 and 2 are as follows. In Tables 1 and 2, aprotic solvents that satisfy condition A are labeled "Aprotic Solvent A," and aprotic solvents that do not satisfy condition A are labeled "Solvent that does not satisfy condition A." (Silicon compounds) BSA: N,O-bis(trimethylsilyl)acetamide (Chemical formula (I) below) TMSI: Trimethylsilylimidazole (Chemical formula (II) below) TMSMo: Trimethylsilylmorpholine (Chemical formula (III) below) TMSMDMA: Trimethylsilyldimethylamine HMDS: Hexamethyldisilazane TMSPy: Trimethylsilylpyrrolidine (Chemical formula (IV) below) TMDS: 1,1,3,3-Tetramethyldisilazane (Chemical formula (V) below) HMCS: 2,2,4,4,6,6-Hexamethylcyclotrisilazane (Chemical formula (VI) below) DVTMDS: 1,3-Divinyl-1,1,3,3-Tetramethyldisilazane (Aprotic solvent) PGMEA: Propylene glycol monomethyl ether acetate DEC : Diethyl carbonate DMC: Dimethyl carbonate DPGMEA: Dipropylene glycol monomethyl ether acetate Note that Novec 7200 refers to a fluorine-based solvent (ethyl nonafluoroisobutyl ether) manufactured by 3M.

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144] The boiling points in Table 1 are those measured by the equilibrium reflux method. However, for BSA and TMSI, the boiling points at 1 atmosphere were estimated using a boiling point conversion chart (Science of Petroleum, Vol. II. p. 1281 (1938)), and the boiling points at 1 atmosphere were used.

[0145]

[0146]

[0147] <Evaluation of the concentration of silicon compounds> A smooth silicon wafer with a thermal oxide film (a Si wafer having a thermal oxide film layer with a thickness of 1 μm on the surface) was cut to a size of 30 mm x 30 mm, immersed in a 1 mass% hydrofluoric acid aqueous solution at 25°C for 10 minutes, then immersed in pure water at 25°C for 1 minute, and after removal, the water on the surface of the silicon wafer was dried to obtain a dry wafer. Next, a total of 1 ml of the chemical solution of the composition was supplied to a heated vaporization chamber and the entire amount of the chemical solution was vaporized. The heating temperature of the vaporization chamber was set below the temperature at which the entire amount of the chemical solution was vaporized and each component contained in the chemical solution did not undergo thermal decomposition. Next, nitrogen gas was supplied to the vaporization chamber at a rate of 2 dm³. ３ The steam was moved from the vaporization chamber to the steam processing chamber by flowing it at a flow rate of 1 / minute. Furthermore, the silicon wafer was placed in the steam processing chamber for 60 seconds with the surface to be processed horizontal and facing downwards (the angle between the normal vector of the surface to be processed on the wafer and the vertical vector was 180°), and a portion of the steam was condensed onto the surface of the silicon wafer. Next, the silicon wafer with the condensate attached was immersed in a petri dish containing 2 g of diethyl carbonate to dissolve the condensate attached to the silicon wafer in the diethyl carbonate. The above operation was repeated 15 times to obtain a diethyl carbonate solution in which the condensate had dissolved. Next, the above diethyl carbonate solution was subjected to gas chromatography analysis (GC-FID analysis), and the area fraction of silicon compounds in the condensate was calculated from the obtained chromatogram using the following formula. Furthermore, GC-FID analysis revealed that all silicon compounds in the diethyl carbonate solution were hydrolyzed during the process of obtaining the aforementioned diethyl carbonate solution. Therefore, the area of ​​the silicon compound hydrolysate peak was used as a substitute for the area of ​​the silicon compound peak. (Area fraction of silicon compounds in the condensate) = S1S / (S1P + S1S) S1S 　 Area of ​​the peak of the hydrolysis product of silicon compounds S1P 　 : Area of ​​solvent peak

[0148] Furthermore, the chemical solution of the composition was subjected to GC-FID measurement, and the area fraction of the silicon compound in the composition was calculated from the resulting chromatogram using the following formula: (Area fraction of silicon compound in the composition) = S²S / (S²P + S²S) 　 : Area of ​​the silicon compound peak S2P 　 : Area of ​​solvent peak

[0149] Finally, the concentration of silicon compounds was calculated using the following formula: (Concentration of silicon compounds) = (Area fraction of silicon compounds in the condensate) / (Area fraction of silicon compounds in the composition)

[0150] The following are the analytical conditions for GC-FID analysis: • Instrument: 8890GC System (Agilent Technologies) • Column: DB-1 0.25 mm × 60 m, film thickness 1.00 μm (J&W) • Detector: FID • Injection volume: 1 μL

[0151] <Evaluation of Water Contact Angle> (1) Cleaning of Silicon Wafer A smooth silicon wafer with a thermal oxide film (a Si wafer having a thermal oxide film layer with a thickness of 1 μm on the surface) was immersed in a 1% by mass hydrofluoric acid aqueous solution at 25°C for 10 minutes, then in pure water at 25°C for 1 minute, and subsequently in 2-propanol (hereinafter referred to as "iPA") at 25°C for 1 minute to prepare an evaluation silicon wafer (with iPA attached).

[0152] (2) Surface treatment of silicon wafer surface by vapor A vapor of the composition was prepared in the same manner as in "Evaluation of the concentration of silicon compounds" described above. The silicon wafer with IPA attached was placed in the vaporization chamber with the surface to be treated facing horizontally and downward, and tilted at 45° from the horizontal (the angle between the normal vector of the surface to be treated and the vertical vector of the wafer was 135°). A portion of the vapor of the composition was condensed onto the silicon wafer surface in the same manner as in "Evaluation of the concentration of silicon compounds" described above, replacing the IPA, and the surface treatment was performed. The surface temperature of the silicon wafer rose with the processing time, but remained below 60°C even after 60 seconds of processing.

[0153] (3) Cleaning of the silicon wafer After that, the silicon wafer was removed from the steam treatment chamber and immersed in iPA at 25°C for 1 minute. Finally, the silicon wafer was removed from the iPA and air was blown onto it to remove the iPA from the surface.

[0154] (4) Measurement of water contact angle of protective film The dried silicon wafer was placed horizontally with the treated surface facing upwards, and 2 μl of pure water was placed on top of it. The angle between the water droplet and the treated surface (water contact angle) was measured at 25°C in air in accordance with JIS R 3257:1999 using a contact angle meter (Kyowa Interface Science Co., Ltd.: CA-X type). The results are shown in Table 1. If the water contact angle in Table 1 was less than 20°, it was determined that no water-repellent protective film had been formed on the surface of the silicon wafer.

[0155] When the surface treatment compositions (chemical solutions) of Examples 1 to 13 were supplied to the wafer surface as vapor compositions, the water contact angles were found to be equivalent to or higher than those of Comparative Examples 1 to 5. Furthermore, when the compositions of Examples 1 to 10 were supplied to the wafer surface as vapor compositions, the concentration of silicon compounds increased compared to Comparative Examples 1 to 2 and 4, resulting in higher water contact angles. In addition, while Comparative Examples 3 and 5 showed high concentrations of silicon compounds, they did not exhibit water contact angles as high as those of Examples 1 to 10.

[0156] This application claims priority based on Japanese Patent Application No. 2024-162403, filed on 19 September 2024, and incorporates all of its disclosures herein.

[0157] 1. Wafer 2. Recessed pattern 3. Protrusion 4. Recess 5. Width of recess 6. Height of protrusion 7. Width of protrusion 8. Liquid 9. Vapor 10. Liquid 11. Protective film

Claims

1. A step of preparing a wafer having an uneven pattern on its surface, a step of supplying a cleaning liquid to the surface of the wafer for cleaning, and a step of supplying vapor of a surface treatment composition to the surface holding the cleaning liquid, causing the vapor to change its state to a liquid on the surface, replacing at least a part of the cleaning liquid with the liquid, and forming a water-repellent protective film on at least a part of the surface. A method for manufacturing a wafer, wherein the surface treatment composition includes at least one silicon compound selected from the group consisting of the following general formula [1], the following general formula [2], and the following general formula [3], and one or more aprotic solvents. R １ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １ is each independently a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, X is each independently a monovalent group in which the atom bonded to the Si atom is nitrogen, oxygen, carbon, or halogen (however, when X is a dialkylamino group, the total carbon number is 5 or more), 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.) (R ２ ｃ Si(H) ３－ｃ ) ３－ｄ NR ３ ｄ [2] (In the above general formula [2], R ２ is each independently a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 5 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, R ３ is each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and the total number of carbon atoms of R ２ and the total number of carbon atoms of R ３ is 5 or less, c is an integer of 1 to 3, and d is 0 or 1.) (In the above general formula [3], R ４ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Y is independently -[(CR ６ ２ ) ｉ -Si(R ４ａ ) ２ ]- (wherein Si is bonded to N in the general formula [3] above), or-[NR ５ａ -Si(R ４ａａ ) ２ ] ｊ - (However, Si is R ４ａａ It can also bond with N or C, and N is R ５ａ (Other than bonding with Si or C), R ４ａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ４ａａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ａ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ６ This is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 9 carbon atoms, where some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, i is between 0 and 9, j is between 0 and 5, and h is an integer between i + 2 × j + 1 (where 1 ≤ h ≤ 10).

2. A method for manufacturing a wafer according to claim 1, wherein the aprotic solvent comprises one or more aprotic solvents A satisfying the following condition A, and the total content of the aprotic solvents A is 70% by mass or more of 100% by mass of the total amount of the aprotic solvent. Condition A: When the boiling point (°C) at 1 atmosphere of at least one of the silicon compounds is PB1, and the boiling point (°C) at 1 atmosphere of the aprotic solvent A is PB2, then (PB1 - PB2) ≥ -10°C is satisfied.

3. A method for manufacturing a wafer according to claim 2, wherein in the surface treatment composition, PB1-PB2, which represents the boiling point difference between the silicon compound and the aprotic solvent A, is 0°C or higher and 160°C or lower.

4. A method for manufacturing a wafer according to claim 2 or 3, wherein the boiling point (PB1) of the silicon compound at 1 atmosphere is 90°C or higher and 250°C or lower.

5. A method for manufacturing a wafer according to claim 2 or 3, wherein the boiling point (PB2) of the aprotic solvent A at 1 atmosphere is 90°C or higher and 240°C or lower.

6. A method for manufacturing a wafer according to claim 1 or 2, wherein the cleaning solution contains a protic solvent.

7. A method for manufacturing a wafer according to claim 1 or 2, wherein the surface treatment composition is catalyst-free or contains a catalyst in an amount of 5% by mass or less per 100% by mass of the surface treatment composition.

8. A wafer manufacturing method according to claim 1 or 2, wherein in the step of forming the water-repellent protective film, the angle between the normal vector of the surface of the wafer and the vertical vector is greater than 0° and less than or equal to 180°.

9. A wafer manufacturing method according to claim 1 or 2, wherein in the step of forming the water-repellent protective film, the vapor of the surface treatment composition to be supplied is obtained by vaporizing the liquid surface treatment composition by at least heat treatment, and the vapor of the surface treatment composition is supplied.

10. A method for manufacturing a wafer according to claim 1 or 2, comprising the step of cleaning at least a portion of the surface of the wafer after the step of forming the water-repellent protective film.

11. A wafer manufacturing method according to claim 1 or 2, comprising the step of cleaning at least a portion of the inside of the chamber supplied with steam after the step of forming the water-repellent protective film.

12. A surface treatment composition for heating and evaporation, used to supply in vapor form to the surface of a wafer holding a cleaning solution, wherein the surface treatment composition comprises at least one silicon compound selected from the group consisting of the following general formulas [1], [2], and [3], and one or more aprotic solvents. １ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １ Each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having nitrogen, oxygen, carbon, or halogen atoms bonded to the Si atom (provided that when X is a dialkylamino group, the total number of carbon atoms is 5 or more); a is an integer from 1 to 3; b is an integer from 0 to 2; and the sum of a and b is 1 to 3. ２ ｃ Si(H) ３－ｃ ) ３－ｄ NR ３ ｄ [2] (In the above general formula [2], R ２ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 5 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ３ Each is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ２ The total number of carbon atoms and R ３ The sum of the total number of carbon atoms is 5 or less, c is an integer from 1 to 3, and d is 0 or 1. (In the above general formula [3], R ４ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Y is independently -[(CR ６ ２ ) ｉ -Si(R ４ａ ) ２ ]- (wherein Si is bonded to N in the general formula [3] above), or-[NR ５ａ -Si(R ４ａａ ) ２ ] ｊ - (However, Si is R ４ａａ It can also bond with N or C, and N is R ５ａ (Other than bonding with Si or C), R ４ａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ４ａａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ａ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ６ This is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 9 carbon atoms, where some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, i is between 0 and 9, j is between 0 and 5, and h is an integer between i + 2 × j + 1 (where 1 ≤ h ≤ 10).

13. A method for using a surface treatment composition, comprising the step of supplying the surface treatment composition in vapor form to the surface of a wafer holding a cleaning solution, wherein the surface treatment composition comprises at least one silicon compound selected from the group consisting of the following general formulas [1], [2], and [3], and one or more aprotic solvents. １ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １ Each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having nitrogen, oxygen, carbon, or halogen atoms bonded to the Si atom (provided that when X is a dialkylamino group, the total number of carbon atoms is 5 or more); a is an integer from 1 to 3; b is an integer from 0 to 2; and the sum of a and b is 1 to 3. ２ ｃ Si(H) ３－ｃ ) ３－ｄ NR ３ ｄ [2] (In the above general formula [2], R ２ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 5 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ３ Each is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ２ The total number of carbon atoms and R ３ The sum of the total number of carbon atoms is 5 or less, c is an integer from 1 to 3, and d is 0 or 1. (In the above general formula [3], R ４ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Y is independently -[(CR ６ ２ ) ｉ -Si(R ４ａ ))- (where Si is bonded to N of the general formula [3]), or -[NR ２ -Si(R ５ａ ))- (where Si is bonded to N or C other than R ４ａａ ), and N is bonded to Si or C other than R ２ )), and R ｊ is a group independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, R ４ａａ is a group independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, R ５ａ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, R ４ａ is a group independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 9 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, i is an integer of 0 to 9, j is an integer of 0 to 5, and h is an integer of i + 2×j + 1 (where 1≦h≦10).)​​​​​​ 14. A vapor composition comprising at least one silicon compound selected from the group consisting of the gaseous following general formula [1], the gaseous following general formula [2], and the gaseous following general formula [3], and one or more kinds of aprotic solvents in gaseous state. R １ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １ is, independently of each other, a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, X is, independently of each other, a monovalent group in which the atom bonded to the Si atom is nitrogen, oxygen, carbon, or halogen (however, when X is a dialkylamino group, the total carbon number is 5 or more), 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.) (R ２ ｃ Si(H) ３－ｃ )) ３－ｄ NR ３ ｄ [2] (In the above general formula [2], R ２ is, independently of each other, a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 5 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, R ３ is, independently of each other, a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and the total number of carbon atoms of R ２ and the total number of carbon atoms of R ３ is 5 or less, c is an integer of 1 to 3, and d is 0 or 1.) (In the above general formula [3], R ４ is, independently of each other, a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, R ５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Y is, independently of each other, -[(CR ６ ２ )) ｉ -Si(R ４ａ )) ２ ]- (wherein Si is bonded to N in the general formula [3] above), or-[NR ５ａ -Si(R ４ａａ ) ２ ] ｊ - (However, Si is R ４ａａ It can also bond with N or C, and N is R ５ａ (Other than bonding with Si or C), R ４ａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ４ａａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ａ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ６ This is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 9 carbon atoms, where some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, i is between 0 and 9, j is between 0 and 5, and h is an integer between i + 2 × j + 1 (where 1 ≤ h ≤ 10).

15. A method for producing a vapor composition, comprising the step of subjecting a liquid surface treatment composition to at least a heat treatment to obtain a vapor composition obtained by vaporizing the liquid surface treatment composition, wherein the surface treatment composition comprises at least one silicon compound selected from the group consisting of the following general formulas [1], [2], and [3], and one or more aprotic solvents. １ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １ Each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms; each of the following groups is independently selected from the group consisting of monovalent hydrocarbon groups having nitrogen, oxygen, carbon, or halogen atoms bonded to the Si atom (provided that when X is a dialkylamino group, the total number of carbon atoms is 5 or more); a is an integer from 1 to 3; b is an integer from 0 to 2; and the sum of a and b is 1 to 3. ２ ｃ Si(H) ３－ｃ ) ３－ｄ NR ３ ｄ [2] (In the above general formula [2], R ２ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 5 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ３ Each is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, and R ２ The total number of carbon atoms and R ３ The sum of the total number of carbon atoms is 5 or less, c is an integer from 1 to 3, and d is 0 or 1. (In the above general formula [3], R ４ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and Y is independently -[(CR ６ ２ ) ｉ -Si(R ４ａ ) ２ ]- (wherein Si is bonded to N in the general formula [3] above), or-[NR ５ａ -Si(R ４ａａ ) ２ ] ｊ - (However, Si is R ４ａａ It can also bond with N or C, and N is R ５ａ (Other than bonding with Si or C), R ４ａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ４ａａ Each of these is independently selected from the group consisting of monovalent hydrocarbon groups having 1 to 10 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, and R ５ａ R is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. ６ This is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 9 carbon atoms, where some or all of the hydrogen atoms may be replaced by fluorine or chlorine atoms, i is between 0 and 9, j is between 0 and 5, and h is an integer between i + 2 × j + 1 (where 1 ≤ h ≤ 10).

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