KR101680438B1

KR101680438B1 - Wafer surface-treatment method and surface-treatment liquid, and surface-treatment agent, surface-treatment liquid, and surface-treatment method for silicon-nitride-containing wafers

Info

Publication number: KR101680438B1
Application number: KR1020147013734A
Authority: KR
Inventors: 마사노리 사이토; 시노부 아라타; 다카시 사이오; 소이치 구몬
Original assignee: 샌트랄 글래스 컴퍼니 리미티드
Priority date: 2011-11-11
Filing date: 2012-10-30
Publication date: 2016-11-28
Also published as: TW201323595A; WO2013069499A1; KR20140080554A

Abstract

Disclosed is a method for surface treatment of a wafer which increases the adhesion between the wafer and the resist by hydrophobizing the surface of the wafer containing the silicon element,
A surface treatment step of bringing a surface treatment liquid for a silicon element-containing wafer into contact with the surface of the wafer to hydrophilize the surface of the wafer,
A process liquid removing step of removing the process liquid from the wafer surface,
A resist film forming step of forming a resist on the wafer surface
Characterized in that, in the surface treatment step, a surface treatment liquid for silicon-containing wafers containing a silicon compound, an acid and a diluting solvent represented by the following general formula (I-1) is used. Way.
[Formula I-1]

[In the formula (I-1), R ¹ is each independently a hydrogen group or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom. X is a monovalent functional group in which an element bonding to the silicon element is nitrogen, and a is an integer of 1 to 3, independently of each other.

Description

TECHNICAL FIELD The present invention relates to a surface treatment method and a surface treatment agent for a silicon nitride-containing wafer, a surface treatment method and a surface treatment agent for a silicon nitride-containing wafer, treatment method for silicon-nitride-containing wafers}

TECHNICAL FIELD The present invention relates to a surface treatment method of a silicon element-containing wafer and a surface treatment solution for a silicon element-containing wafer, which improves the adhesion between a resist and a silicon element-containing wafer in semiconductor device production and the like. The present invention also relates to a surface treatment agent for wafers, a surface treatment solution, and a surface treatment method of the wafer which improve the adhesion between a resist containing silicon nitride and a wafer in semiconductor device production or the like.

In the manufacture of a semiconductor chip, a fine resist pattern is formed on the surface of a silicon wafer through lithography, etching, or the like after forming a resist film. Further, the wafer surface is etched using the resist pattern as a mold, and a concavo-convex pattern is formed on the wafer surface. It has been known that the adhesiveness between the resist and the wafer surface is often insufficient in the film formation of the resist, so that the adhesion can be improved by hydrophobizing the surface of the wafer using a silane coupling agent such as HMDS before the resist is formed For example, Patent Document 1). By performing the film formation of the resist after this treatment, adhesion between the wafer and the resist is improved and a good resist pattern can be formed. However, since the contact area between the wafer and the resist becomes smaller as the pattern becomes finer, the adhesion between the wafer and the resist is required to be higher. If the adhesion is insufficient, there arises a problem of peeling or falling of the resist pattern. In the immersion lithography corresponding to the miniaturization of the pattern, it is particularly problematic that the resist tends to peel off during immersion. The hydrophobicity of the surface of the wafer is further improved to improve the adhesion between the wafer and the resist. Therefore, the improvement of the hydrophobicity of the surface of the wafer using various silane coupling agents has been investigated (see, for example, Patent Document 2 , 3).

As a method of hydrophobizing the wafer, there are a method of immersing the wafer in a treatment liquid containing a silane coupling agent, a treatment liquid containing a silane coupling agent such as a method of spinning a treatment liquid containing a silane coupling agent on the wafer, (Steam-prime method), or the like (see, for example, Patent Document 1), or a method of spraying a gas obtained by bubbling a silane coupling agent with a gas such as nitrogen onto a surface of a wafer in a heated state (steam prime method). However, in consideration of the treatment performance of a silane coupling agent, a steam prime method which can be treated in a short time is generally used (for example, Patent Documents 2 and 3).

Furthermore, in recent years, there has been a demand for hydrophobic treatment of wafers containing silicon nitride, which is difficult to perform silane coupling treatment with respect to silicon oxide, in accordance with diversification of wafer materials. However, there have been no surface treating solutions capable of imparting excellent hydrophobicity to the surface of silicon nitride.

Japanese Patent Publication No. 47-026043 Japanese Patent Application Laid-Open No. 09-102458 Japanese Patent Application Laid-Open No. 2007-19465

&Lt; First aspect &

The adhesion of a wafer containing a silicon element (hereinafter sometimes referred to as a " silicon element-containing wafer " or simply " wafer ") and a resist can be improved by sufficiently hydrophobizing the wafer surface. In order to hydrophobize the surface of the wafer, it is necessary to bond a compound having a hydrophobic property with a reaction active site such as a hydroxyl group existing on the wafer surface. In the prior art, the hydrophobicization of the wafer is carried out by a method (steam-prime method) in which a gas obtained by bubbling a silane coupling agent with a gas such as nitrogen is sprayed on a heated wafer surface. This is because the reactivity of the silane coupling agent with the treatment liquid containing the silane coupling agent and the method of contacting the wafer is low so that the hydrophobic surface of the wafer can not be sufficiently hydrophobic or a long time is required for exhibiting sufficient hydrophobicity on the surface of the wafer Therefore, in order to solve the problem, it is necessary to adopt a steam prime method which easily exhibits sufficient hydrophobicity on the wafer surface in a short time. However, such a method requires a special apparatus (chamber) for vaporizing the silane coupling agent, and there is a problem in that the throughput is bad because it needs to be treated in batches in the apparatus. In addition, since it is necessary to heat the wafer, the energy loss is large. The present invention relates to a surface treatment method of a silicon element-containing wafer capable of enhancing adhesion between a wafer and a resist by hydrophobizing the surface of the wafer containing silicon elements having little energy loss and improved throughput without requiring a special apparatus, (Hereinafter sometimes referred to as a " surface treatment liquid " or simply a " treatment liquid ") for an element-containing wafer.

In the second aspect,

The adhesion between the wafer and the resist can be improved by sufficiently hydrophobizing the wafer surface. In order to hydrophobize the surface of the wafer, it is necessary to bond a compound having a hydrophobic property with a reaction active site such as a hydroxyl group existing on the wafer surface. In the case of wafers containing silicon nitride (hereinafter sometimes referred to as "silicon nitride-containing wafers", "silicon nitride wafers", or simply "wafers"), since the number of hydroxyl groups present on the wafer surface is small, It is difficult to impart sufficient hydrophobicity to the wafer and the adhesion between the wafer and the resist can not be enhanced. The present invention relates to a silicon nitride-containing surface treatment agent (hereinafter sometimes referred to as a "surface treatment agent" or simply "treatment agent") capable of improving adhesion between a wafer and a resist by hydrophobizing the silicon nitride-containing wafer surface, A surface treatment liquid (hereinafter sometimes referred to as a " surface treatment liquid " or simply a " treatment liquid ") and a surface treatment method of silicon nitride-containing wafers.

&Lt; First aspect &

The present invention relates to a method for surface treatment of a wafer which improves adhesion between the wafer and resist by hydrophobizing the surface of the wafer containing the silicon element,

A surface treatment step of bringing a surface treatment liquid for a silicon element-containing wafer into contact with the surface of the wafer to hydrophilize the surface of the wafer,

A process liquid removing step of removing the process liquid from the wafer surface,

A resist film forming step of forming a resist on the wafer surface

Characterized in that, in the surface treatment step, a surface treatment liquid for silicon-containing wafers containing a silicon compound, an acid and a diluting solvent represented by the following general formula (I-1) is used. Method.

[Formula I-1]

Preferably, the surface treatment step comprises spinning the silicon element-containing wafer with the treatment liquid or immersing the silicon element-containing wafer in the treatment liquid.

The present invention also relates to a surface treatment liquid for a silicon element-containing wafer used in a surface treatment method for a silicon element-containing wafer, which comprises a silicon compound represented by the following formula I-1, an acid and a diluting solvent It is a surface treatment liquid for silicon element-containing wafers.

[Formula I-1]

The silicon compound is preferably a silicon compound represented by the following general formula (I-2).

[Formula I-2]

[In the formula I-2, R ¹ and X are each the same as in the general formula I-1.]

The silicon compound is preferably a silicon compound represented by the following general formula (I-3).

[Formula I-3]

[In the formula I-3, R ² is a hydrocarbon group having 4 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom. X is the same as in formula I-1.]

The number of carbon atoms of R ² in the general formula I-3 is preferably 6 to 18.

The acid contained in the surface treatment solution for a silicon element-containing wafer is preferably an organic acid.

The silicon compound is preferably contained in an amount of 0.1 to 50 mass% with respect to 100 mass% of the total amount of the surface treatment liquid for a silicon element-containing wafer.

In the second aspect,

The present invention relates to a silicon nitride-containing wafer surface treatment agent for improving the adhesiveness between a wafer and a resist by hydrophobizing the surface of the wafer before depositing a resist on the wafer surface containing silicon nitride, wherein the treating agent is represented by the following formula II-1 Wherein the silicon nitride compound is a silicon compound.

[Formula II-1]

[In the formula (II-1), R ¹ is independently a hydrogen group or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom. In Formula II-1, the total number of carbon atoms contained as R ¹ is 6 or more. X is at least one group selected from a monovalent functional group in which an element bonding with a silicon element is nitrogen, a monovalent functional group in which an element bonding with a silicon element is oxygen, and a halogen group, and a is an integer of 1 to 3, .]

The silicon compound is preferably a silicon compound represented by the following formula (II-2).

[Formula II-2]

[R ¹ and X in the formula II-2 are respectively the same as those in the formula II-1]

The silicon compound is preferably a silicon compound represented by the following Formula II-3.

[Formula II-3]

[In the formula (II-3), R ² is a hydrocarbon group having 4 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom. X is the same as in formula II-1.]

The silicon compound is preferably a silicon compound represented by the following formula (II-4).

[Formula II-4]

[In the formula (II-4), R ³ is a hydrocarbon group having 4 to 18 carbon atoms in which at least a part of hydrogen atoms are substituted with halogen atoms, and Y is a halogen group.]

A surface treatment liquid for a silicon nitride-containing wafer obtained by dissolving the surface treatment agent for silicon nitride-containing wafers in a diluting solvent, wherein 0.1 to 50 mass% of the silicon compound is contained relative to a total amount of 100 mass% Containing wafers.

And a silicon nitride-containing surface treatment liquid obtained by dissolving the surface treatment agent for silicon nitride-containing wafers and an acid in a diluting solvent, characterized in that the silicon compound is contained in an amount of 0.1 to 50 mass% with respect to a total amount of 100 mass% Containing silicon nitride-containing surface treatment liquid.

It is also preferable that the silicon compound in the surface treatment solution for silicon nitride-containing wafers containing the acid is a silicon compound represented by the following general formula (II-5).

[Formula II-5]

[In the formula II-5, R ⁴ is a hydrocarbon group having 4 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom. Z is a monovalent functional group whose element bonding with the silicon element is nitrogen or a monovalent functional group whose oxygen element bonding with the silicon element is oxygen.]

The number of carbon atoms of R ^{4 in} the formula II-5 is preferably 6 to 18.

It is preferable that Z in the general formula II-5 is a monovalent functional group whose element bonding to the silicon element is nitrogen.

The present invention also relates to a method for surface treatment of a wafer which improves adhesion between the wafer and resist by hydrophobizing the surface of the wafer containing silicon nitride,

A surface treatment agent for a silicon nitride-containing wafer or a surface treatment solution for a silicon nitride-containing wafer is brought into contact with the surface of the wafer, or a surface treatment agent for a silicon nitride-containing wafer or a silicon nitride-containing wafer is brought into contact with the surface of the wafer, A surface treatment process,

A resist film forming step of forming a resist on the wafer surface

Wherein the surface treatment agent for silicon nitride-containing wafers or the surface treatment liquid for silicon nitride-containing wafers described in any one of the above is used in the surface treatment step.

It is preferable that the surface of the wafer is subjected to hydrophobic treatment by bringing the surface treatment liquid for silicon nitride containing wafer into contact with the surface of the wafer in the surface treatment step.

By using the surface treatment method of the silicon element-containing wafer and the silicon element-containing wafer surface treatment solution of the present invention, it is possible to impart hydrophobicity to the surface of the wafer including the silicon element without using a special device. As a result, It is possible to reduce the energy loss accompanying the surface treatment for hydrophobicization of the wafer surface and improve the throughput of the treatment.

Further, by using the surface treatment agent for silicon nitride-containing wafers, the surface treatment liquid and the surface treatment method of the wafer of the present invention, it is possible to impart good hydrophobicity to the surface of the wafer including silicon nitride. Therefore, it is expected that the silicon nitride-containing wafer subjected to hydrophobicity using the surface treatment agent, the surface treatment liquid and the surface treatment method of the wafer of the present invention of the present invention has good adhesion with the resist.

&Lt; First aspect &

BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described in more detail below in view of the first aspect. The wafer including the silicon element subjected to the surface treatment using the treatment liquid of the present invention can be obtained by forming a silicon oxide film on a silicon wafer or a silicon wafer by a thermal oxidation method, a CVD method, a sputtering method, Or a polysilicon film and a silicon oxide film, a polysilicon film, or a silicon wafer surface are naturally oxidized. Further, wafers composed of a plurality of components including silicon and / or silicon oxide, silicon carbide wafers, and various films including silicon elements on wafers may be used as wafers. Further, various films including a silicon element may be formed on a wafer not including a silicon element such as a sapphire wafer, various compound semiconductor wafers, and a plastic wafer. In addition, the treatment liquid can hydrophobicize a wafer surface including a silicon element, a film surface including a silicon element formed on the wafer, and a wafer on which a pattern including a silicon element formed from the wafer and the film is formed. Further, the surface of the silicon element-containing wafer may be cleaned before the surface treatment of the silicon element-containing wafer of the present invention. Examples of the cleaning liquid used for the cleaning include water, an organic solvent, a mixture of water and an organic solvent, and an acid or base dissolved in them. The silicon element-containing wafer may be immersed in the cleaning liquid as the cleaning, or the spin element may be subjected to a spin treatment for cleaning the wafers one by one by supplying the cleaning liquid near the center of rotation while rotating and holding the silicon element-containing wafer substantially horizontally. The cleaning liquid may be used in a heated state.

A resist film forming step of forming a resist on the wafer surface

, Characterized in that a surface treatment liquid for silicon-containing wafers containing a silicon compound, an acid and a diluting solvent represented by the general formula I-1 is used in the surface treatment step Method.

In the surface treatment step, the surface of the wafer is made hydrophobic by bringing the surface treatment liquid for a silicon element-containing wafer into contact with the surface of the wafer. The method of contacting the surface of the wafer with the surface treatment liquid for silicon element-containing wafers is not limited, but it is preferable to spin-treat the silicon element-containing wafer with the treatment solution or immerse the silicon element-containing wafer in the treatment solution.

The spin processing is a method in which wafers are processed one by one by supplying liquid to the vicinity of the rotation center while keeping the wafers substantially horizontally rotated, for example. The immersion treatment is, for example, a method in which a plurality of wafers are immersed in an immersion tank of a surface treatment liquid for a silicon element-containing wafer at one time. The surface treatment liquid for silicon element-containing wafers of the present invention can be applied to the above-described spin treatment or immersion treatment because it is possible to impart sufficient hydrophobicity to the surface of the wafer in a short time even by a surface treatment method in which a liquid and a wafer are brought into contact with each other . Further, when the above-described spin treatment is performed using the surface treatment liquid for silicon element-containing wafers of the present invention, the continuous process from the surface treatment step to the resist film formation step can be continuously performed, leading to a simplification of the production process.

In addition, the hydrophobic property imparted to the surface of the wafer by the surface treatment method using the surface treatment liquid for a silicon element-containing wafer of the present invention may or may not necessarily be uniformly applied continuously. However, It is more preferable that they are continuously and homogeneously applied to each other.

In the surface treatment step, if the temperature of the treatment liquid is increased, the surface of the wafer can be easily hydrophobicized in a shorter time. However, if the temperature of the treatment liquid is excessively increased, the stability of the treatment liquid may be impaired due to boiling or evaporation of the surface treatment liquid. Therefore, the treatment liquid is preferably maintained at 10 to 160 캜, Lt; 0 > C.

In the process liquid removing step, the surface treatment liquid for the silicon element-containing wafers is removed from the surface of the hydrophobized wafer. A method of removing the treatment liquid from the surface of the wafer may be a method of removing the treatment liquid from the surface of the wafer and replacing the treatment liquid on the surface of the wafer with a solvent or water different from the treatment liquid and drying the solvent or water from the wafer surface . Known drying methods such as spin drying, IPA (2-propanol) steam drying, Marangoni drying, hot drying, hot air drying and vacuum drying can be applied to the drying. The surface of the wafer is replaced with the solvent or water, and the solvent or water is replaced with a resist before curing used in the resist film-forming step of the next step, whereby the surface treatment step, the treatment liquid removing step and the resist film- You can do it. In this case, if the surface treatment step is performed by spinning, and the subsequent treatment liquid removing step and the resist film forming step are also performed by the same spinning treatment, since the surface treatment step to the resist film forming step can be continuously performed as described above, Can be expected to improve.

A resist film forming step for forming a resist film on the surface of the hydrophobized wafer after the process liquid removing process is performed. The film formation method of the resist is not particularly limited, and a known method can be used. For example, a spin-film-forming process in which a resist is cured before the cure is formed while keeping the wafer substantially horizontally while rotating it, and a resist is formed on the wafer surface one by one.

In the manufacture of a semiconductor chip, after forming a resist film, a pattern is formed on the wafer surface through the following operation. That is, after the resist film forming step is performed, a pattern is formed on the resist, and then a pattern is formed on the wafer surface. The method is not particularly limited as long as a pattern is formed. As a general method, a resist is applied to the surface of a wafer in a resist film forming step, the resist is exposed through a resist mask, and the exposed or unexposed resist is removed by etching A resist having a desired pattern is prepared. Also, a resist having a pattern can be obtained by pressing the mold having the pattern on the resist. Subsequently, the wafer is etched. At this time, concave portions of the resist pattern are selectively etched. Finally, when the resist is peeled off, a silicon wafer having a pattern is obtained.

Further, the present invention relates to a surface treatment liquid for a silicon element-containing wafer used in a surface treatment method for a silicon element-containing wafer, which comprises a silicon compound represented by the above general formula I-1, an acid and a diluting solvent It is a surface treatment liquid for silicon element-containing wafers.

The hydrocarbon group represented by R ¹ of the silicon compound represented by the general formula I-1 is a hydrophobic group, and the surface of the treated wafer becomes a good hydrophobic surface. Hydrophobicity can be exhibited not only on the surface of silicon oxide or the like having a large number of hydroxyl groups per unit area by the hydrophobic group but also on the surface of silicon nitride having a small number of hydroxyl groups per unit area. The reactive group X is a functional group for reacting with the hydroxyl group present on the surface of the wafer to form a siloxane bond with the silicon element on the surface of the wafer. It is possible to chemically react the silicon compound and the hydroxyl group on the surface of the wafer in a short period of time even if the process liquid and the wafer are brought into contact with each other by using the surface treatment liquid for wafers containing the silicon compound, It is possible to impart hydrophobicity to the wafer surface.

As the silicon compound of formula I-1, for example _{(CH 3) 3 SiNH 2,} C 2 H 5 (CH 3) 2 SiNH 2, C 3 H 7 (CH 3) 2 SiNH 2, C 4 H _{9 (CH 3) 2 SiNH 2} , C 5 H 11 (CH 3) 2 SiNH 2, C 6 H 13 (CH 3) 2 SiNH 2, C 7 H 15 (CH 3) 2 SiNH 2, C 8 H 17 ( _{CH 3) 2 SiNH 2, C} 9 H 19 (CH 3) 2 SiNH 2, C 10 H 21 (CH 3) 2 SiNH 2, C 11 H 23 (CH 3) 2 SiNH 2, C 12 H 25 (CH 3 _{) 2 SiNH 2, C 13 H} 27 (CH 3) 2 SiNH 2, C 14 H 29 (CH 3) 2 SiNH 2, C 15 H 31 (CH 3) 2 SiNH 2, C 16 H 33 (CH 3) 2 _{SiNH 2, C 17 H 35 (} CH 3) 2 SiNH 2, C 18 H 37 (CH 3) 2 SiNH 2, CF 3 C 2 H 4 (CH 3) 2 SiNH 2, C 2 F 5 C 2 H 4 ( _{CH 3) 2 SiNH 2, C} 3 F 7 C 2 H 4 (CH 3) 2 SiNH 2, C 4 F 9 C 2 H 4 (CH 3) 2 SiNH 2, C 5 F 11 C 2 H 4 (CH 3 _{) 2 SiNH 2, C 6 F} 13 C 2 H 4 (CH 3) 2 SiNH 2, C 7 F 15 C 2 H 4 (CH 3) 2 SiNH 2, C 8 F 17 C 2 H 4 (CH 3) 2 _{SiNH 2, [(CH 3)} 3 Si] 2 NH, [C 2 H 5 (CH 3) 2 Si] 2 NH, [C 3 H 7 (CH 3) 2 Si] 2 NH, [C 4 H 9 ( CH ₃ ) ₂ Si] ₂ NH, [C ₅ H ₁₁ (CH ₃ ) ₂ Si] ₂ NH, [C _{6 H 13 (CH 3) 2} Si] 2 NH, [C 7 H 15 (CH 3) 2 Si] 2 NH, [C 8 H 17 (CH 3) 2 Si] 2 NH, [C 9 H 19 (CH _{3) 2 Si] 2 NH,} [C 10 H 21 (CH 3) 2 Si] 2 NH, [C 11 H 23 (CH 3) 2 Si] 2 NH, [C 12 H 25 (CH 3) 2 Si] _{2 NH, [C 13 H 27} (CH 3) 2 Si] 2 NH, [C 14 H 29 (CH 3) 2 Si] 2 NH, [C 15 H 31 (CH 3) 2 Si] 2 NH, [C _{16 H 33 (CH 3) 2} Si] 2 NH, [C 17 H 35 (CH 3) 2 Si] 2 NH, [C 18 H 37 (CH 3) 2 Si] 2 NH, [CF 3 C 2 H 4 _{(CH 3) 2 Si] 2} NH, [C 2 F 5 C 2 H 4 (CH 3) 2 Si] 2 NH, [C 3 F 7 C 2 H 4 (CH 3) 2 Si] 2 NH, [C _{4 F 9 C 2 H 4 (} CH 3) 2 Si] 2 NH, [C 5 F 11 C 2 H 4 (CH 3) 2 Si] 2 NH, [C 6 F 13 C 2 H 4 (CH 3) 2 _{Si] 2 NH, [C 7} F 15 C 2 H 4 (CH 3) 2 Si] 2 NH, [C 8 F 17 C 2 H 4 (CH 3) 2 Si] 2 NH, [CH 3 (C 2 H _{5) 2 Si] 2 NH,} [(C 2 H 5) 3 Si] 2 NH, [C 3 H 7 (C 2 H 5) 2 Si] 2 NH, [C 4 H 9 (C 2 H 5) 2 _{Si] 2 NH, [C 5} H 11 (C 2 H 5) 2 Si] 2 NH, [C 6 H 13 (C 2 H 5) 2 Si] 2 NH, [C 7 H 15 (C 2 H 5) _{2 Si] 2 NH, [C} 8 H 17 (C 2 H 5) 2 Si] 2 NH, [C 9 H 19 (C 2 H 5) 2 Si] 2 NH, [C 10 H 21 (C 2 H 5 ) ₂ S _{i] 2 NH, [C 11} H 23 (C 2 H 5) 2 Si] 2 NH, [C 12 H 25 (C 2 H 5) 2 Si] 2 NH, [C 13 H 27 (C 2 H 5) _{2 Si] 2 NH, [C} 14 H 29 (C 2 H 5) 2 Si] 2 NH, [C 15 H 31 (C 2 H 5) 2 Si] 2 NH, [C 16 H 33 (C 2 H 5 _{) 2 Si] 2 NH, [} C 17 H 35 (C 2 H 5) 2 Si] 2 NH, [C 18 H 37 (C 2 H 5) 2 Si] 2 NH, [(CH 3) 3 Si] 3 _{N, [C 2 H 5 (} CH 3) 2 Si] 3 N, [C 3 H 7 (CH 3) 2 Si] 3 N, [C 4 H 9 (CH 3) 2 Si] 3 N, [C 5 _{H 11 (CH 3) 2 Si} ] 3 N, [C 6 H 13 (CH 3) 2 Si] 3 N, [C 7 H 15 (CH 3) 2 Si] 3 N, [C 8 H 17 (CH 3 _{) 2 Si] 3 N, [} C 9 H 19 (CH 3) 2 Si] 3 N, [C 10 H 21 (CH 3) 2 Si] 3 N, [C 11 H 23 (CH 3) 2 Si] 3 _{N, [C 12 H 25 (} CH 3) 2 Si] 3 N, [C 13 H 27 (CH 3) 2 Si] 3 N, [C 14 H 29 (CH 3) 2 Si] 3 N, [C 15 _{H 31 (CH 3) 2 Si} ] 3 N, [C 16 H 33 (CH 3) 2 Si] 3 N, [C 17 H 35 (CH 3) 2 Si] 3 N, [C 18 H 37 (CH 3 _{) 2 Si] 3 N, [} CF 3 C 2 H 4 (CH 3) 2 Si] 3 N, [C 2 F 5 C 2 H 4 (CH 3) 2 Si] 3 N, [C 3 F 7 C 2 _{H 4 (CH 3) 2 Si} ] 3 N, [C 4 F 9 C 2 H 4 (CH 3) 2 Si] 3 N, [C 5 F 11 C 2 H 4 (CH 3) 2 Si] 3 N, [C ₆ F ₁₃ C ₂ H ₄ (CH _{3) 2 Si] 3 N,} [C 7 F 15 C 2 H 4 (CH 3) 2 Si] 3 N, [C 8 F 17 C 2 H 4 (CH 3) 2 Si] 3 N, (CH 3) _{3 SiN (CH 3) 2,} C 2 H 5 (CH 3) 2 SiN (CH 3) 2, C 3 H 7 (CH 3) 2 SiN (CH 3) 2, C 4 H 9 (CH 3) 2 SiN _{(CH 3) 2, C 5} H 11 (CH 3) 2 SiN (CH 3) 2, C 6 H 13 (CH 3) 2 SiN (CH 3) 2, C 7 H 15 (CH 3) 2 SiN (CH _{3) 2, C 8 H 17} (CH 3) 2 SiN (CH 3) 2, C 9 H 19 (CH 3) 2 SiN (CH 3) 2, C 10 H 21 (CH 3) 2 SiN (CH 3) _{2, C 11 H 23 (CH} 3) 2 SiN (CH 3) 2, C 12 H 25 (CH 3) 2 SiN (CH 3) 2, C 13 H 27 (CH 3) 2 SiN (CH 3) 2, _{C 14 H 29 (CH 3)} 2 SiN (CH 3) 2, C 15 H 31 (CH 3) 2 SiN (CH 3) 2, C 16 H 33 (CH 3) 2 SiN (CH 3) 2, C 17 _{H 35 (CH 3) 2 SiN} (CH 3) 2, C 18 H 37 (CH 3) 2 SiN (CH 3) 2, (CH 3) 2 HSiN (CH 3) 2, C 2 H 5 (CH 3) _{HSiN (CH 3) 2, C} 3 H 7 (CH 3) HSiN (CH 3) 2, C 4 H 9 (CH 3) HSiN (CH 3) 2, C 5 H 11 (CH 3) HSiN (CH 3) _{2, C 6 H 13 (CH} 3) HSiN (CH 3) 2, C 7 H 15 (CH 3) HSiN (CH 3) 2, C 8 H 17 (CH 3) HSiN (CH 3) 2, C 9 H _{19 (CH 3) HSiN (CH} 3) 2, C 10 H 21 (CH 3) HSiN (C _{H 3) 2, C 11 H} 23 (CH 3) HSiN (CH 3) 2, C 12 H 25 (CH 3) HSiN (CH 3) 2, C 13 H 27 (CH 3) HSiN (CH 3) 2, _{C 14 H 29 (CH 3)} HSiN (CH 3) 2, C 15 H 31 (CH 3) HSiN (CH 3) 2, C 16 H 33 (CH 3) HSiN (CH 3) 2, C 17 H 35 ( _{CH 3) HSiN (CH 3)} 2, C 18 H 37 (CH 3) HSiN (CH 3) 2, CF 3 C 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 2 F 5 C 2 H _{4 (CH 3) 2 SiN (} CH 3) 2, C 3 F 7 C 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 4 F 9 C 2 H 4 (CH 3) 2 SiN (CH 3 _{) 2, C 5 F 11 C} 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 6 F 13 C 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 7 F 15 C 2 H _{4 (CH 3) 2 SiN (} CH 3) 2, C 8 F 17 C 2 H 4 ((CH 3) 2 SiN (CH 3) 2, (C 2 H 5) 3 SiN (CH 3) 2, C 3 _{H 7 (C 2 H 5)} 2 SiN (CH 3) 2, C 4 H 9 (C 2 H 5) 2 SiN (CH 3) 2, C 5 H 11 (C 2 H 5) 2 SiN (CH 3) _{2, C 6 H 13 (C} 2 H 5) 2 SiN (CH 3) 2, C 7 H 15 (C 2 H 5) 2 SiN (CH 3) 2, C 8 H 17 (C 2 H 5) 2 SiN _{(CH 3) 2, C 9} H 19 (C 2 H 5) 2 SiN (CH 3) 2, C 10 H 21 (C 2 H 5) 2 SiN (CH 3) 2, C 11 H 23 (C 2 H ₅ ) ₂ SiN (CH ₃ ) ₂ , C ₁₂ H ₂₅ (C ₂ H ₅ ) ₂ SiN (CH ₃ ) ₂ _{, C 13 H 27 (C 2} H 5) 2 SiN (CH 3) 2, C 14 H 29 (C 2 H 5) 2 SiN (CH 3) 2, C 15 H 31 (C 2 H 5) 2 SiN ( _{CH 3) 2, C 16 H} 33 (C 2 H 5) 2 SiN (CH 3) 2, C 17 H 35 (C 2 H 5) 2 SiN (CH 3) 2, C 18 H 37 (C 2 H 5 _{) 2 SiN (CH 3) 2} , (C 4 H 9) 3 SiN (CH 3) 2, C 5 H 11 (C 4 H 9) 2 SiN (CH 3) 2, C 6 H 13 (C 4 H 9 _{) 2 SiN (CH 3) 2} , C 7 H 15 (C 4 H 9) 2 SiN (CH 3) 2, C 8 H 17 (C 4 H 9) 2 SiN (CH 3) 2, C 9 H 19 ( _{C 4 H 9) 2 SiN (} CH 3) 2, C 10 H 21 (C 4 H 9) 2 SiN (CH 3) 2, C 11 H 23 (C 4 H 9) 2 SiN (CH 3) 2, C _{12 H 25 (C 4 H 9} ) 2 SiN (CH 3) 2, C 13 H 27 (C 4 H 9) 2 SiN (CH 3) 2, C 14 H 29 (C 4 H 9) 2 SiN (CH 3 _{) 2, C 15 H 31 (} C 4 H 9) 2 SiN (CH 3) 2, C 16 H 33 (C 4 H 9) 2 SiN (CH 3) 2, C 17 H 35 (C 4 H 9) 2 _{SiN (CH 3) 2, C} 18 H 37 (C 4 H 9) 2 SiN (CH 3) 2, (CH 3) 2 Si [N (CH 3) 2] 2, C 2 H 5 (CH 3) Si _{[N (CH 3) 2]} 2, C 3 H 7 (CH 3) Si [N (CH 3) 2] 2, C 4 H 9 (CH 3) Si [N (CH 3) 2] 2, C 5 _{H 11 (CH 3) Si [} N (CH 3) 2] 2, C 6 H 13 (CH 3) Si [N (CH 3) 2] 2, C 7 H 1 _{5 (CH 3) Si [N} (CH 3) 2] 2, C 8 H 17 (CH 3) Si [N (CH 3) 2] 2, C 9 H 19 (CH 3) Si [N (CH 3) _{2] 2, C 10 H 21} (CH 3) Si [N (CH 3) 2] 2, C 11 H 23 (CH 3) Si [N (CH 3) 2] 2, C 12 H 25 (CH 3) _{Si [N (CH 3) 2} ] 2, C 13 H 27 (CH 3) Si [N (CH 3) 2] 2, C 14 H 29 (CH 3) Si [N (CH 3) 2] 2, C _{15 H 31 (CH 3) Si} [N (CH 3) 2] 2, C 16 H 33 (CH 3) Si [N (CH 3) 2] 2, C 17 H 35 (CH 3) Si [N (CH _{3) 2] 2, C 18} H 37 (CH 3) Si [N (CH 3) 2] 2, CF 3 C 2 H 4 (CH 3) Si [N (CH 3) 2] 2, C 2 F 5 _{C 2 H 4 (CH 3)} Si [N (CH 3) 2] 2, C 3 F 7 C 2 H 4 (CH 3) Si [N (CH 3) 2] 2, C 4 F 9 C 2 H 4 _{(CH 3) Si [N (} CH 3) 2] 2, C 5 F 11 C 2 H 4 (CH 3) Si [N (CH 3) 2] 2, C 6 F 13 C 2 H 4 (CH 3) _{Si [N (CH 3) 2} ] 2, C 7 F 15 C 2 H 4 (CH 3) Si [N (CH 3) 2] 2, C 8 F 17 C 2 H 4 (CH 3) Si [N ( _{CH 3) 2] 2, CH} 3 Si [N (CH 3) 2] 3, C 2 H 5 Si [N (CH 3) 2] 3, C 3 H 7 Si [N (CH 3) 2] 3, _{C 4 H 9 Si [N (} CH 3) 2] 3, C 5 H 11 Si [N (CH 3) 2] 3, C 6 H 13 Si [N (CH 3) 2] 3, C 7 H 15 Si _{[N (CH 3) 2]} 3, C 8 H 17 Si [N (CH 3) 2] _{3, C 9 H 19 Si [} N (CH 3) 2] 3, C 10 H 21 Si [N (CH 3) 2] 3, C 11 H 23 Si [N (CH 3) 2] 3, C 12 H _{25 Si [N (CH 3)} 2] 3, C 13 H 27 Si [N (CH 3) 2] 3, C 14 H 29 Si [N (CH 3) 2] 3, C 15 H 31 Si [N ( _{CH 3) 2] 3, C} 16 H 33 Si [N (CH 3) 2] 3, C 17 H 35 Si [N (CH 3) 2] 3, C 18 H 37 Si [N (CH 3) 2] _{3, CF 3 C 2 H 4} Si [N (CH 3) 2] 3, C 2 F 5 C 2 H 4 Si [N (CH 3) 2] 3, C 3 F 7 C 2 H 4 Si [N ( _{CH 3) 2] 3, C} 4 F 9 C 2 H 4 Si [N (CH 3) 2] 3, C 5 F 11 C 2 H 4 Si [N (CH 3) 2] 3, C 6 F 13 C _{2 H 4 Si [N (CH} 3) 2] 3, C 7 F 15 C 2 H 4 Si [N (CH 3) 2] 3, C 8 F 17 C 2 H 4 Si [N (CH 3) 2] _{3, (CH 3) 3 SiN} (C 2 H 5) 2, C 2 H 5 (CH 3) 2 SiN (C 2 H 5) 2, C 3 H 7 (CH 3) 2 SiN (C 2 H 5) _{2, C 4 H 9 (CH} 3) 2 SiN (C 2 H 5) 2, C 5 H 11 (CH 3) 2 SiN (C 2 H 5) 2, C 6 H 13 (CH 3) 2 SiN (C _{2 H 5) 2, C 7} H 15 (CH 3) 2 SiN (C 2 H 5) 2, C 8 H 17 (CH 3) 2 SiN (C 2 H 5) 2, C 9 H 19 (CH 3) _{2 SiN (C 2 H 5)} 2, C 10 H 21 (CH 3) 2 SiN (C 2 H 5) 2, C 11 H 23 (CH 3) 2 SiN (C 2 H 5) 2, C 12 H 25 ( _{CH 3) 2 SiN (C 2} H 5) 2, C 13 H 27 (CH 3) 2 SiN (C 2 H 5) 2, C 14 H 29 (CH 3) 2 SiN (C 2 H 5) 2, C _{15 H 31 (CH 3) 2} SiN (C 2 H 5) 2, C 16 H 33 (CH 3) 2 SiN (C 2 H 5) 2, C 17 H 35 (CH 3) 2 SiN (C 2 H 5 _{) 2, C 18 H 37 (} CH 3) 2 SiN (C 2 H 5) 2, CF 3 C 2 H 4 (CH 3) 2 SiN (C 2 H 5) 2, C 2 F 5 C 2 H 4 ( _{CH 3) 2 SiN (C 2} H 5) 2, C 3 F 7 C 2 H 4 (CH 3) 2 SiN (C 2 H 5) 2, C 4 F 9 C 2 H 4 (CH 3) 2 SiN ( _{C 2 H 5) 2, C} 5 F 11 C 2 H 4 (CH 3) 2 SiN (C 2 H 5) 2, C 6 F 13 C 2 H 4 (CH 3) 2 SiN (C 2 H 5) 2 _{, C 7 F 15 C 2 H} 4 (CH 3) 2 SiN (C 2 H 5) 2, C 8 F 17 C 2 H 4 (CH 3) 2 SiN (C 2 H 5) 2, (C 2 H 5 _{) 3 SiN (C 2 H 5} ) 2, C 3 H 7 (C 2 H 5) 2 SiN (C 2 H 5) 2, C 4 H 9 (C 2 H 5) 2 SiN (C 2 H 5) 2 _{, C 5 H 11 (C 2} H 5) 2 SiN (C 2 H 5) 2, C 6 H 13 (C 2 H 5) 2 SiN (C 2 H 5) 2, C 7 H 15 (C 2 H 5 _{) 2 SiN (C 2 H 5} ) 2, C 8 H 17 (C 2 H 5) 2 SiN (C 2 H 5) 2, C 9 H 19 (C 2 H 5) 2 SiN (C 2 H 5) 2 _{, C 10 H 21 (C 2} H 5) 2 SiN (C 2 H 5) 2, C 11 H 23 (C 2 H 5) 2 SiN (C 2 H 5) 2, C _{12 H 25 (C 2 H 5} ) 2 SiN (C 2 H 5) 2, C 13 H 27 (C 2 H 5) 2 SiN (C 2 H 5) 2, C 14 H 29 (C 2 H 5) 2 _{SiN (C 2 H 5) 2} , C 15 H 31 (C 2 H 5) 2 SiN (C 2 H 5) 2, C 16 H 33 (C 2 H 5) 2 SiN (C 2 H 5) 2, C _{17 H 35 (C 2 H 5} ) 2 SiN (C 2 H 5) 2, C 18 H 37 (C 2 H 5) 2 SiN (C 2 H 5) 2, (C 4 H 9) 3 SiN (C 2 _{H 5) 2, C 5 H} 11 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 6 H 13 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 7 H 15 ( _{C 4 H 9) 2 SiN (} C 2 H 5) 2, C 8 H 17 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 9 H 19 (C 4 H 9) 2 SiN (C 2 _{H 5) 2, C 10 H} 21 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 11 H 23 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 12 H 25 ( _{C 4 H 9) 2 SiN (} C 2 H 5) 2, C 13 H 27 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 14 H 29 (C 4 H 9) 2 SiN (C 2 _{H 5) 2, C 15 H} 31 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 16 H 33 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 17 H 35 ( Aminosilane compounds such as C ₄ H ₉ ) ₂ SiN (C ₂ H ₅ ) ₂ , and C ₁₈ H ₃₇ (C ₄ H ₉ ) ₂ SiN (C ₂ H ₅ ) ₂ and silazane compounds.

Further, for example, _{(CH 3) 3 SiNCO, C} 2 H 5 (CH 3) 2 SiNCO, C 3 H 7 (CH 3) 2 SiNCO, C 4 H 9 (CH 3) 2 SiNCO, C 5 H 11 (CH _{3) 2 SiNCO, C 6 H} 13 (CH 3) 2 SiNCO, C 7 H 15 (CH 3) 2 SiNCO, C 8 H 17 (CH 3) 2 SiNCO, C 9 H 19 (CH 3) 2 SiNCO, C _{10 H 21 (CH 3) 2} SiNCO, C 11 H 23 (CH 3) 2 SiNCO, C 12 H 25 (CH 3) 2 SiNCO, C 13 H 27 (CH 3) 2 SiNCO, C 14 H 29 (CH 3 _{) 2 SiNCO, C 15 H 31} (CH 3) 2 SiNCO, C 16 H 33 (CH 3) 2 SiNCO, C 17 H 35 (CH 3) 2 SiNCO, C 18 H 37 (CH 3) 2 SiNCO, CF 3 C ₂ H ₄ (CH ₃ ) ₂ SiNCO, C ₂ F ₅ C ₂ H ₄ (CH ₃ ) ₂ SiNCO, C ₃ F ₇ C ₂ H ₄ (CH ₃ ) ₂ SiNCO, C ₄ F ₉ C ₂ H ₄ _{CH 3) 2 SiNCO, C 5} F 11 C 2 H 4 (CH 3) 2 SiNCO, C 6 F 13 C 2 H 4 (CH 3) 2 SiNCO, C 7 F 15 C 2 H 4 (CH 3) 2 SiNCO _{, C 8 F 17 C 2 H} 4 (CH 3) 2 SiNCO, (C 2 H 5) 3 SiNCO, C 3 H 7 (C 2 H 5) 2 SiNCO, C 4 H 9 (C 2 H 5) 2 SiNCO , C ₅ H ₁₁ (C ₂ H ₅ ) ₂ SiNCO, C ₆ H ₁₃ (C ₂ H ₅ ) ₂ SiNCO, C ₇ H ₁₅ (C ₂ H ₅ ) ₂ SiNCO, C ₈ H ₁₇ (C ₂ H ₅ ) ₂ SiNCO, C ₉ H ₁₉ (C ₂ H ₅ ) ₂ SiNCO, C ₁₀ H ₂₁ (C ₂ H ₅ ) ₂ SiNCO , C ₁₁ H ₂₃ (C ₂ H ₅ ) ₂ SiNCO, C ₁₂ H ₂₅ (C ₂ H ₅ ) ₂ SiNCO, C ₁₃ H ₂₇ (C ₂ H ₅ ) ₂ SiNCO, C ₁₄ H ₂₉ (C ₂ H ₅ ) _{2 SiNCO, C 15 H 31 (} C 2 H 5) 2 SiNCO, C 16 H 33 (C 2 H 5) 2 SiNCO, C 17 H 35 (C 2 H 5) 2 SiNCO, C 18 H 37 (C 2 H _{5) 2 SiNCO, (C 4} H 9) 3 SiNCO, C 5 H 11 (C 4 H 9) 2 SiNCO, C 6 H 13 (C 4 H 9) 2 SiNCO, C 7 H 15 (C 4 H 9) _{2 SiNCO, C 8 H 17 (} C 4 H 9) 2 SiNCO, C 9 H 19 (C 4 H 9) 2 SiNCO, C 10 H 21 (C 4 H 9) 2 SiNCO, C 11 H 23 (C 4 H ₉ ) ₂ SiNCO, C ₁₂ H ₂₅ (C ₄ H ₉ ) ₂ SiNCO, C ₁₃ H ₂₇ (C ₄ H ₉ ) ₂ SiNCO, C ₁₄ H ₂₉ (C ₄ H ₉ ) ₂ SiNCO, C ₁₅ H ₃₁ _{4 H 9) 2 SiNCO, C} 16 H 33 (C 4 H 9) 2 SiNCO, C 17 H 35 (C 4 H 9) 2 SiNCO, C 18 H 37 (C 4 H 9) 2 SiNCO, (CH 3) _{2 Si (NCO) 2, C} 2 H 5 (CH 3) Si (NCO) 2, C 3 H 7 (CH 3) Si (NCO) 2, C 4 H 9 (CH 3) Si (NCO) 2, C _{5 H 11 (CH 3) Si} (NCO) 2, C 6 H 13 (CH 3) Si (NCO) 2, C 7 H 15 (CH 3) Si (NCO) 2, C 8 H 17 (CH 3) Si _{(NCO) 2, C 9 H} 19 (CH 3) Si (NCO) 2, C 10 H 21 (CH 3) Si (NCO) 2, C 11 H 23 (CH 3) Si (NCO) 2, C 12 H ₂₅ (CH ₃₎ Si (NC _{O) 2, C 13 H 27} (CH 3) Si (NCO) 2, C 14 H 29 (CH 3) Si (NCO) 2, C 15 H 31 (CH 3) Si (NCO) 2, C 16 H 33 _{(CH 3) Si (NCO)} 2, C 17 H 35 (CH 3) Si (NCO) 2, C 18 H 37 (CH 3) Si (NCO) 2, CF 3 C 2 H 4 (CH 3) Si ( _{NCO) 2, C 2 F 5} C 2 H 4 (CH 3) Si (NCO) 2, C 3 F 7 C 2 H 4 (CH 3) Si (NCO) 2, C 4 F 9 C 2 H 4 (CH _{3) Si (NCO) 2,} C 5 F 11 C 2 H 4 (CH 3) Si (NCO) 2, C 6 F 13 C 2 H 4 (CH 3) Si (NCO) 2, C 7 F 15 C 2 _{H 4 (CH 3) Si (} NCO) 2, C 8 F 17 C 2 H 4 (CH 3) Si (NCO) 2, CH 3 Si (NCO) 3, C 2 H 5 Si (NCO) 3, C 3 _{H 7 Si (NCO) 3,} C 4 H 9 Si (NCO) 3, C 5 H 11 Si (NCO) 3, C 6 H 13 Si (NCO) 3, C 7 H 15 Si (NCO) 3, C 8 _{H 17 Si (NCO) 3,} C 9 H 19 Si (NCO) 3, C 10 H 21 Si (NCO) 3, C 11 H 23 Si (NCO) 3, C 12 H 25 Si (NCO) 3, C 13 _{H 27 Si (NCO) 3,} C 14 H 29 Si (NCO) 3, C 15 H 31 Si (NCO) 3, C 16 H 33 Si (NCO) 3, C 17 H 35 Si (NCO) 3, C 18 _{H 37 Si (NCO) 3,} CF 3 C 2 H 4 Si (NCO) 3, C 2 F 5 C 2 H 4 Si (NCO) 3, C 3 F 7 C 2 H 4 Si (NCO) 3, C 4 F ₉ C ₂ H ₄ Si (NCO) ₃ , C ₅ F ₁₁ C ₂ H ₄ Si (NCO) ₃ , C ₆ F ₁₃ C ₂ H ₄ Si NCO) ₃ , C ₇ F ₁₅ C ₂ H ₄ Si (NCO) ₃ , and C ₈ F ₁₇ C ₂ H ₄ Si (NCO) ₃ .

When the hydrogen atom of the hydrocarbon group is substituted by a halogen atom among these silicon compounds, the halogen atom to be substituted is preferably a fluorine atom in consideration of hydrophobicity.

Further, the monovalent functional group having an element bonding with the silicon element represented by X in the general formula I-1 is nitrogen may be a carbon, hydrogen, boron, nitrogen, phosphorus, oxygen, sulfur, silicon, germanium, fluorine, chlorine, bromine, iodine and when the functional group consisting of the elements, for example -NHSi (CH _{3) 3} _{group, -NHSi (CH 3) 2 C} 4 H 9 _{group, -NHSi (CH 3) 2 C} 8 H 17 group, -N ( CH ₃₎ ₂ _{groups, -N (C 2 H 5)} 2 _{groups, -N (C 3 H 7)} 2 _{groups, -N (CH 3) (C} 2 H 5) groups, -NH (C ₂ H ₅₎ An -NCO group, an imidazole group, and an acetamide group.

When a is 1 or 2, when the treatment liquid is stored for a long period of time, polymerization of the silicon compound occurs due to incorporation of water or the like, and insoluble matter Or the effect of imparting hydrophobicity of the treatment liquid may deteriorate, so that there is a possibility that the storable period becomes short. For this reason, it is preferable that a in the general formula I-1 is 3 (that is, the silicon compound represented by the general formula I-2) in view of the usable time of the treatment liquid.

Also, of the silicon compounds represented by the general formula I-1, those in which R ¹ is a non-substituted hydrocarbon group having 4 to 18 carbon atoms or a hydrocarbon group in which a hydrogen atom may be substituted with a halogen atom and 2 methyl groups Is preferred because the reaction rate with the hydroxyl group on the surface of the wafer is fast. This is because the steric hindrance caused by the hydrophobic group greatly affects the reaction rate in the reaction of the hydroxyl group on the wafer surface with the silicon compound, and the alkyl chain bonded to the silicon element is preferably the shorter one except for the longest one . The use of a silicon compound having such a structure tends to impart excellent hydrophobicity to the surface of the wafer and is preferable because hydrophobicity can be imparted to a surface such as silicon nitride having a small amount of hydroxyl groups per unit area.

When the carbon number of R ² in the general formula I-3 is 6 to 18, the effect of imparting hydrophobicity to the wafer surface is more preferable. Use of the above-mentioned treatment liquid is preferable because it is easier to impart hydrophobicity to the surface of the surface such as silicon nitride which has fewer hydroxyl groups as reaction active sites.

The silicon compound is preferably contained in an amount of 0.1 to 50% by mass based on 100% by mass of the total amount of the treatment liquid of the present invention, more preferably 0.3 to 20% by mass based on 100% by mass of the total amount of the treatment liquid. When the content of the silicon compound is less than 0.1% by mass, it is likely to react with moisture contained in a diluting solvent in a small amount and to be inactivated, so that the ability to perform the hydrophobic treatment is insufficient and the surface of the wafer may not be sufficiently hydrophobic. On the other hand, if it is more than 50% by mass, there is a fear of remaining as impurities on the surface of the wafer.

The treatment liquid of the present invention may contain two or more kinds of silicon compounds represented by the above-mentioned general formula I-1, and may contain other than the silicon compound represented by the above general formula I-1 and the silicon compound represented by the above general formula I-1 Of silicon compounds may be contained.

The treatment liquid of the present invention contains an acid. The presence of the acid accelerates the reaction between the silicon compound and the hydroxyl group on the surface of the wafer. As such an acid, it is possible to use an acid such as trifluoroacetic acid, trifluoroacetic acid anhydride, pentafluoropropionic acid, pentafluoropropionic anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, sulfuric acid, You can pick up mountains. Particularly, considering the promoting effect of the reaction, acids such as trifluoroacetic acid, trifluoroacetic acid anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic acid anhydride, sulfuric acid and hydrogen chloride are preferable, and the acid includes water . Particularly, organic acids such as trifluoroacetic acid, trifluoroacetic acid anhydride, trifluoromethane sulfonic acid and trifluoromethane sulfonic acid anhydride are preferable considering the catalytic effect and solubility in an organic solvent, and the acid includes water .

The addition amount of the acid is preferably 0.01 to 100% by mass based on 100% by mass of the total amount of the silicon compound. If the addition amount is decreased, the catalytic effect is lowered, which is not preferable. In addition, even when added in excess, the catalytic effect is not improved, and when the amount is larger than that of the silicon compound, the catalytic effect may be lowered inversely. There is also a risk of remaining on the wafer surface as an impurity. Therefore, the amount of the acid added is preferably 0.01 to 100 mass%, more preferably 0.1 to 50 mass%, based on 100 mass% of the total amount of the silicon compound.

Further, the treatment liquid of the present invention contains a diluting solvent. The diluting solvent is not particularly limited as long as it dissolves the silicon compound and the acid. Examples of the diluting solvent include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, lactone solvents, carbonate solvents, alcohols, An organic solvent such as an alcohol derivative or a nitrogen element-containing solvent is suitably used. When water is used as a diluting solvent, there is a possibility that a reactive site (X in the above-mentioned general formula I-1) of the silicon compound in the treatment liquid is hydrolyzed by water to produce a silanol group (Si-OH). Since the reactive site also reacts with the silanol group, there is a possibility that silicon compounds are bonded together to form a dimer. Since the reactivity of the dimer with the hydroxyl group on the surface of the wafer is low, there is a possibility that the time required for hydrophobizing the surface of the wafer is prolonged. Therefore, it is not preferable to use water as a diluting solvent.

In addition, since the silicon compound is easily reacted with the protonic solvent, the use of an aprotic solvent as the organic solvent is particularly preferable because hydrophobicity is easily exhibited in a short time. The aprotic solvent refers to both aprotic polar solvent and aprotic non-polar solvent. Examples of the aprotic solvent include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, lactone-based solvents, carbonate-based solvents, derivatives of polyhydric alcohols not having a hydroxyl group, Containing solvent. Examples of the hydrocarbons include toluene, benzene, xylene, hexane, heptane, and octane. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetate. Examples of the ethers include diethyl ether, Examples of the ketones include acetone, acetyl acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, and the like. The halogen-containing solvent For example, perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene and the like, 1,1,1,3,3-pentafluorobutane, Hydrofluorocarbons such as octafluorocyclopentane, 2,3-dihydrodecafluoropentane and Aurora H (manufactured by Japan Zeon Co., Ltd.), hydrofluorocarbons such as methyl perfluoroisobutyl (Manufactured by Asahi Glass Co., Ltd.), Novec7100, Novec7200, Novec7300 and Novec7600 (all manufactured by 3M Co.), methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, Asahikawa AE- , Chlorofluorocarbons such as tetrachloromethane and the like, hydrochlorofluorocarbons such as chloroform and the like, chlorofluorocarbons such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3,3- 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3, 3,3-trifluoropropene and the like, perfluoroether, perfluoropolyether and the like. Examples of the sulfoxide-based solvent include dimethylsulfoxide and the like, and the lactone-based solvent Examples include? -Butyrolactone,? -Valerolactone,? -Hexanolactone,? -Heptanoclock T-butyrolactone, 隆 -hexanolactone, 隆 -hexanolactone, 隆 -hexanolactone, 隆 -hexanolactone, 隆 -hexanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, ε-hexanolactone, etc. Examples of the carbonate-based solvent include dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, Propylene carbonate, etc. Examples of the polyhydric alcohol derivative having no hydroxyl group include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethyl Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diisobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, Triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol diacetate, tetraethylene glycol monoethyl ether acetate, triethylene glycol monoethyl ether acetate, Ethylene 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 diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Butyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl Ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol Recycled 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, and glycerin triacetate. Examples of the nitrogen element-containing solvent having no NH bond include N, N-dimethylformamide, N, Amide, N-methyl-2-pyrrolidone, triethylamine, pyridine and the like.

If a part or all of the diluting solvent is nonflammable, it is preferable that the treatment liquid becomes incombustible or the flash point becomes high and the risk of the treatment liquid lowers. Since halogen-containing solvents are often non-flammable, non-flammable halogen-containing solvents can be suitably used as nonflammable diluting solvents. In addition, according to the "International Harmonization System for Classification and Labeling of Chemicals: GHS", a solvent whose flash point is 93 ° C or less is defined as a "flammable liquid". Therefore, even if a non-flammable solvent is not used, a solvent having a flash point exceeding 93 ° C. as the diluting solvent tends to be 93 ° C. or higher in the treatment liquid, so that the treatment liquid is less likely to be a "flammable liquid" desirable.

In addition, lactone-based solvents, carbonate-based solvents and polyhydric alcohol derivatives often have a high flash point, so that use of such a solvent as a solvent makes it possible to lower the risk of the treatment liquid. Specifically, from the viewpoint of safety, there may be mentioned γ-butyrolactone having a flash point exceeding 93 캜,? -Hexanolactone,? -Heptanolactone,? -Octanolactone,? -Nonanolactone,? -Decanolactone, ? -undecanolactone,? -undecanolactone,? -undecanolactone,? -undecanolactone,? -undecanolactone,? -valerolactone,? -hexanolactone,? -octanolactone,? -nonanolactone,? -decanolactone, Diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol isomonobutyl ether, diethylene glycol butyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Dibutyl ether, diethylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol Triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether, Ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol mono Butyl ether, 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 diacetate, dipropylene glycol diacetate, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol Monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tri Propylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol monomethyl ether acetate, It is more preferable to use, as the solvent, phenol glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, and glycerin triacetate.

The diluting solvent may also be present in a trace amount of water. However, if this water is contained in a large amount in a solvent, the silicon compound may be hydrolyzed by the water to lower the reactivity. Therefore, the water content in the solvent is preferably lowered, and the water content thereof is preferably less than 1 molar ratio with respect to the silicon compound when mixed with the silicon compound, particularly preferably less than 0.5 molar.

In the second aspect,

The present invention will be described in more detail below in view of the second aspect. First, the surface treatment agent for silicon nitride-containing wafers provided in the present invention is a surface treatment agent for silicon nitride-containing wafers which improves the adhesion between the wafer and the resist by treating the surface of the wafer before depositing a resist on the surface of the wafer containing silicon nitride. The surface treatment agent is a surface treatment agent for hydrophobizing the surface of a silicon nitride-containing wafer, and the treatment agent is a silicon compound represented by the following general formula (II-1).

[Formula II-1]

When the surface of the silicon nitride-containing wafer is subjected to a surface treatment using a treatment liquid containing a silicon compound having a large hydrophobic group, the hydrocarbon group represented by R ¹ is a hydrophobic group, the surface of the wafer after treatment shows good hydrophobicity. If the total number of at least 6 carbon atoms is contained as R ¹ in the formula II-1 can be a hydrophobic wafer surface containing the silicon nitride sufficiently.

In the silicon compound represented by the general formula II-1, the functional group represented by X, which is a reactive site thereof, can chemically react with the hydroxyl group on the surface of the wafer. As a result, the silicon element of the silicon compound reacts with the silicon element It is possible to impart hydrophobicity to the surface of the wafer.

As the silicon compound of formula II-1, for example, _{C 4 H 9 (CH 3)} 2 SiCl, C 5 H 11 (CH 3) 2 SiCl, C 6 H 13 (CH 3) 2 SiCl, C 7 _{H 15 (CH 3) 2 SiCl} , C 8 H 17 (CH 3) 2 SiCl, C 9 H 19 (CH 3) 2 SiCl, C 10 H 21 (CH 3) 2 SiCl, C 11 H 23 (CH 3) _{2 SiCl, C 12 H 25 (} CH 3) 2 SiCl, C 13 H 27 (CH 3) 2 SiCl, C 14 H 29 (CH 3) 2 SiCl, C 15 H 31 (CH 3) 2 SiCl, C 16 H _{33 (CH 3) 2 SiCl,} C 17 H 35 (CH 3) 2 SiCl, C 18 H 37 (CH 3) 2 SiCl, C 5 H 11 (CH 3) HSiCl, C 6 H 13 (CH 3) HSiCl, _{C 7 H 15 (CH 3)} HSiCl, C 8 H 17 (CH 3) HSiCl, C 9 H 19 (CH 3) HSiCl, C 10 H 21 (CH 3) HSiCl, C 11 H 23 (CH 3) HSiCl, _{C 12 H 25 (CH 3)} HSiCl, C 13 H 27 (CH 3) HSiCl, C 14 H 29 (CH 3) HSiCl, C 15 H 31 (CH 3) HSiCl, C 16 H 33 (CH 3) HSiCl, _{C 17 H 35 (CH 3)} HSiCl, C 18 H 37 (CH 3) HSiCl, C 2 F 5 C 2 H 4 (CH 3) 2 SiCl, C 3 F 7 C 2 H 4 (CH 3) 2 SiCl, _{C 4 F 9 C 2 H 4} (CH 3) 2 SiCl, C 5 F 11 C 2 H 4 (CH 3) 2 SiCl, C 6 F 13 C 2 H 4 (CH 3) 2 SiCl, C 7 F 15 C ₂ H ₄ (CH ₃ ) ₂ SiCl, C ₈ F ₁₇ C ₂ _{H 4 (CH 3) 2 SiCl} , (C 2 H 5) 3 SiCl, C 3 H 7 (C 2 H 5) 2 SiCl, C 4 H 9 (C 2 H 5) 2 SiCl, C 5 H 11 (C _{2 H 5) 2 SiCl, C} 6 H 13 (C 2 H 5) 2 SiCl, C 7 H 15 (C 2 H 5) 2 SiCl, C 8 H 17 (C 2 H 5) 2 SiCl, C 9 H 19 _{(C 2 H 5) 2 SiCl} , C 10 H 21 (C 2 H 5) 2 SiCl, C 11 H 23 (C 2 H 5) 2 SiCl, C 12 H 25 (C 2 H 5) 2 SiCl, C 13 _{H 27 (C 2 H 5)} 2 SiCl, C 14 H 29 (C 2 H 5) 2 SiCl, C 15 H 31 (C 2 H 5) 2 SiCl, C 16 H 33 (C 2 H 5) 2 SiCl, C ₁₇ H ₃₅ (C ₂ H ₅ ) ₂ SiCl, C ₁₈ H ₃₇ (C ₂ H ₅ ) ₂ SiCl, CF ₃ C ₂ H ₄ (C ₂ H ₅ ) ₂ SiCl, C ₂ F ₅ C ₂ H ₄ C ₂ H ₅ ) ₂ SiCl, C ₃ F ₇ C ₂ H ₄ (C ₂ H ₅ ) ₂ SiCl, C ₄ F ₉ C ₂ H ₄ (C ₂ H ₅ ) ₂ SiCl, C ₅ F ₁₁ C ₂ H ₄ (C ₂ H ₅ ) ₂ SiCl, C ₆ F ₁₃ C ₂ H ₄ (C ₂ H ₅ ) ₂ SiCl, C ₇ F ₁₅ C ₂ H ₄ (C ₂ H ₅ ) ₂ SiCl, C ₈ F ₁₇ C ₂ H _{4 (C 2 H 5) 2} SiCl, (C 4 H 9) 3 SiCl, C 5 H 11 (C 4 H 9) 2 SiCl, C 6 H 13 (C 4 H 9) 2 SiCl, C 7 H 15 ( _{C 4 H 9) 2 SiCl,} C 8 H 17 (C 4 H 9) 2 SiCl, C 9 H 19 (C 4 H 9) 2 SiCl, C 10 H 21 (C 4 H 9) 2 SiCl, C 11 H ₂₃ (C ₄ H ₉ ) ₂ SiCl, C ₁₂ H _{2 5 (C 4 H 9) 2} SiCl, C 13 H 27 (C 4 H 9) 2 SiCl, C 14 H 29 (C 4 H 9) 2 SiCl, C 15 H 31 (C 4 H 9) 2 SiCl, C ₁₆ H ₃₃ (C ₄ H ₉ ) ₂ SiCl, C ₁₇ H ₃₅ (C ₄ H ₉ ) ₂ SiCl, C ₁₈ H ₃₇ (C ₄ H ₉ ) ₂ SiCl, CF ₃ C ₂ H ₄ (C ₄ H ₉ ) _{2 SiCl, C 2 F 5 C} 2 H 4 (C 4 H 9) 2 SiCl, C 3 F 7 C 2 H 4 (C 4 H 9) 2 SiCl, C 4 F 9 C 2 H 4 (C 4 H 9 _{) 2 SiCl, C 5 F 11} C 2 H 4 (C 4 H 9) 2 SiCl, C 6 F 13 C 2 H 4 (C 4 H 9) 2 SiCl, C 7 F 15 C 2 H 4 (C 4 H ₉ ) ₂ SiCl, C ₈ F ₁₇ C ₂ H ₄ (C ₄ H ₉ ) ₂ SiCl, C ₅ H ₁₁ (CH ₃ ) SiCl ₂ , C ₆ H ₁₃ (CH ₃ ) SiCl ₂ , C ₇ H ₁₅ _{3) SiCl 2, C 8 H} 17 (CH 3) SiCl 2, C 9 H 19 (CH 3) SiCl 2, C 10 H 21 (CH 3) SiCl 2, C 11 H 23 (CH 3) SiCl 2, C _{12 H 25 (CH 3) SiCl} 2, C 13 H 27 (CH 3) SiCl 2, C 14 H 29 (CH 3) SiCl 2, C 15 H 31 (CH 3) SiCl 2, C 16 H 33 (CH 3 _{) SiCl 2, C 17 H 35} (CH 3) SiCl 2, C 18 H 37 (CH 3) SiCl 2, C 3 F 7 C 2 H 4 (CH 3) SiCl 2, C 4 F 9 C 2 H 4 ( _{CH 3) SiCl 2, C 5} F 11 C 2 H 4 (CH 3) SiCl 2, C 6 F 13 C 2 H 4 (CH 3) SiCl 2, C 7 F 15 C 2 H 4 (CH 3) SiCl 2 , C ₈ F ₁₇ C ₂ H ₄ (CH ₃ ) SiCl ₂ , C ₆ H ₁₃ SiCl ₃ , C ₇ H ₁₅ SiCl ₃ , C ₈ H ₁₇ SiCl ₃ , C ₉ H ₁₉ SiCl ₃ , C ₁₀ H ₂₁ SiCl ₃ , C ₁₁ H ₂₃ SiCl ₃ , C ₁₂ H ₂₅ SiCl ₃ , C ₁₃ H ₂₇ SiCl ₃ , C ₁₄ H ₂₉ SiCl ₃ , C ₁₅ H ₃₁ SiCl ₃ , C ₁₆ H ₃₃ SiCl ₃ , C ₁₇ H ₃₅ SiCl ₃ , C ₁₈ H ₃₇ SiCl ₃ , C ₄ F ₉ C ₂ H ₄ SiCl ₃ , C ₅ F ₁₁ C ₂ H ₄ SiCl ₃ , C ₆ F ₁₃ C ₂ H ₄ SiCl ₃ , C ₇ F ₁₅ C ₂ H ₄ SiCl ₃ , C ₈ F ₁₇ C ₂ H ₄ SiCl _3, and the like.

Also, for example, an alkoxysilane compound in which the chloro group of the chlorosilane compound is substituted with an alkoxy group such as a methoxy group or an ethoxy group, or an isocyanate silane compound substituted with an isocyanate group.

Further, for example, _{C 4 H 9 (CH 3)} 2 SiNH 2, C 5 H 11 (CH 3) 2 SiNH 2, C 6 H 13 (CH 3) 2 SiNH 2, C 7 H 15 (CH 3) 2 SiNH _{2, C 8 H 17 (CH} 3) 2 SiNH 2, C 9 H 19 (CH 3) 2 SiNH 2, C 10 H 21 (CH 3) 2 SiNH 2, C 11 H 23 (CH 3) 2 SiNH 2, _{C 12 H 25 (CH 3)} 2 SiNH 2, C 13 H 27 (CH 3) 2 SiNH 2, C 14 H 29 (CH 3) 2 SiNH 2, C 15 H 31 (CH 3) 2 SiNH 2, C 16 _{H 33 (CH 3) 2 SiNH} 2, C 17 H 35 (CH 3) 2 SiNH 2, C 18 H 37 (CH 3) 2 SiNH 2, C 5 H 11 (CH 3) HSiNH 2, C 6 H 13 ( _{CH 3) HSiNH 2, C 7} H 15 (CH 3) HSiNH 2, C 8 H 17 (CH 3) HSiNH 2, C 9 H 19 (CH 3) HSiNH 2, C 10 H 21 (CH 3) HSiNH 2, _{C 11 H 23 (CH 3)} HSiNH 2, C 12 H 25 (CH 3) HSiNH 2, C 13 H 27 (CH 3) HSiNH 2, C 14 H 29 (CH 3) HSiNH 2, C 15 H 31 (CH _{3) HSiNH 2, C 16 H} 33 (CH 3) HSiNH 2, C 17 H 35 (CH 3) HSiNH 2, C 18 H 37 (CH 3) HSiNH 2, C 2 F 5 C 2 H 4 (CH 3) _{2 SiNH 2, C 3 F 7} C 2 H 4 (CH 3) 2 SiNH 2, C 4 F 9 C 2 H 4 (CH 3) 2 SiNH 2, C 5 F 11 C 2 H 4 (CH 3) 2 SiNH _{2, C 6 F 13 C 2} H 4 (CH 3) 2 SiNH 2, C _{7 F 15 C 2 H 4 (} CH 3) 2 SiNH 2, C 8 F 17 C 2 H 4 (CH 3) 2 SiNH 2, (C 2 H 5) 3 SiNH 2, C 3 H 7 (C 2 H 5 _{) 2 SiNH 2, C 4 H} 9 (C 2 H 5) 2 SiNH 2, C 5 H 11 (C 2 H 5) 2 SiNH 2, C 6 H 13 (C 2 H 5) 2 SiNH 2, C 7 H _{15 (C 2 H 5) 2} SiNH 2, C 8 H 17 (C 2 H 5) 2 SiNH 2, C 9 H 19 (C 2 H 5) 2 SiNH 2, C 10 H 21 (C 2 H 5) 2 _{SiNH 2, C 11 H 23 (} C 2 H 5) 2 SiNH 2, C 12 H 25 (C 2 H 5) 2 SiNH 2, C 13 H 27 (C 2 H 5) 2 SiNH 2, C 14 H 29 ( _{C 2 H 5) 2 SiNH 2} , C 15 H 31 (C 2 H 5) 2 SiNH 2, C 16 H 33 (C 2 H 5) 2 SiNH 2, C 17 H 35 (C 2 H 5) 2 SiNH 2 _{, C 18 H 37 (C 2} H 5) 2 SiNH 2, (C 4 H 9) 3 SiNH 2, C 5 H 11 (C 4 H 9) 2 SiNH 2, C 6 H 13 (C 4 H 9) 2 _{SiNH 2, C 7 H 15 (} C 4 H 9) 2 SiNH 2, C 8 H 17 (C 4 H 9) 2 SiNH 2, C 9 H 19 (C 4 H 9) 2 SiNH 2, C 10 H 21 ( _{C 4 H 9) 2 SiNH 2} , C 11 H 23 (C 4 H 9) 2 SiNH 2, C 12 H 25 (C 4 H 9) 2 SiNH 2, C 13 H 27 (C 4 H 9) 2 SiNH 2 _{, C 14 H 29 (C 4} H 9) 2 SiNH 2, C 15 H 31 (C 4 H 9) 2 SiNH 2, C 16 H 33 (C 4 H 9) 2 SiNH 2, C 1 _{7 H 35 (C 4 H 9} ) 2 SiNH 2, C 18 H 37 (C 4 H 9) 2 SiNH 2, [C 4 H 9 (CH 3) 2 Si] 2 NH, [C 5 H 11 (CH 3 _{) 2 Si] 2 NH, [} C 6 H 13 (CH 3) 2 Si] 2 NH, [C 7 H 15 (CH 3) 2 Si] 2 NH, [C 8 H 17 (CH 3) 2 Si] 2 _{NH, [C 9 H 19 (} CH 3) 2 Si] 2 NH, [C 10 H 21 (CH 3) 2 Si] 2 NH, [C 11 H 23 (CH 3) 2 Si] 2 NH, [C 12 _{H 25 (CH 3) 2 Si} ] 2 NH, [C 13 H 27 (CH 3) 2 Si] 2 NH, [C 14 H 29 (CH 3) 2 Si] 2 NH, [C 15 H 31 (CH 3 _{) 2 Si] 2 NH, [} C 16 H 33 (CH 3) 2 Si] 2 NH, [C 17 H 35 (CH 3) 2 Si] 2 NH, [C 18 H 37 (CH 3) 2 Si] 2 NH, [C ₂ F ₅ C ₂ H ₄ (CH ₃ ) ₂ Si] ₂ NH, [C ₃ F ₇ C ₂ H ₄ (CH ₃ ) ₂ Si] ₂ NH, [C ₄ F ₉ C ₂ H ₄ _{CH 3) 2 Si] 2 NH} , [C 5 F 11 C 2 H 4 (CH 3) 2 Si] 2 NH, [C 6 F 13 C 2 H 4 (CH 3) 2 Si] 2 NH, [C 7 _{F 15 C 2 H 4 (CH} 3) 2 Si] 2 NH, [C 8 F 17 C 2 H 4 (CH 3) 2 Si] 2 NH, [(C 2 H 5) 3 Si] 2 NH, [C _{3 H 7 (C 2 H 5} ) 2 Si] 2 NH, [C 4 H 9 (C 2 H 5) 2 Si] 2 NH, [C 5 H 11 (C 2 H 5) 2 Si] 2 NH, [ _{C 6 H 13 (C 2 H} 5) 2 Si] 2 NH, [C 7 H 15 (C 2 H 5) 2 Si] 2 NH, [C 8 H 17 (C 2 H 5) 2 Si] 2 NH _{, [C 9 H 19 (C} 2 H 5) 2 Si] 2 NH, [C 10 H 21 (C 2 H 5) 2 Si] 2 NH, [C 11 H 23 (C 2 H 5) 2 Si] 2 _{NH, [C 12 H 25 (} C 2 H 5) 2 Si] 2 NH, [C 13 H 27 (C 2 H 5) 2 Si] 2 NH, [C 14 H 29 (C 2 H 5) 2 Si] _{2 NH, [C 15 H 31} (C 2 H 5) 2 Si] 2 NH, [C 16 H 33 (C 2 H 5) 2 Si] 2 NH, [C 17 H 35 (C 2 H 5) 2 Si ] ₂ NH, [C ₁₈ H ₃₇ (C ₂ H ₅ ) ₂ Si] ₂ NH, [CF ₃ C ₂ H ₄ (C ₂ H ₅ ) ₂ Si] ₂ NH, [C ₂ F ₅ C ₂ H ₄ C ₂ H ₅ ) ₂ Si] ₂ NH, [C ₃ F ₇ C ₂ H ₄ (C ₂ H ₅ ) ₂ Si] ₂ NH, [C ₄ F ₉ C ₂ H ₄ (C ₂ H ₅ ) ₂ Si] _{2 NH, [C 5 F 11} C 2 H 4 (C 2 H 5) 2 Si] 2 NH, [C 6 F 13 C 2 H 4 (C 2 H 5) 2 Si] 2 NH, [C 7 F 15 _{C 2 H 4 (C 2 H} 5) 2 Si] 2 NH, [C 8 F 17 C 2 H 4 (C 2 H 5) 2 Si] 2 NH, [C 4 H 9 (CH 3) 2 Si] 3 _{N, [C 5 H 11 (} CH 3) 2 Si] 3 N, [C 6 H 13 (CH 3) 2 Si] 3 N, [C 7 H 15 (CH 3) 2 Si] 3 N, [C 8 _{H 17 (CH 3) 2 Si} ] 3 N, [C 9 H 19 (CH 3) 2 Si] 3 N, [C 10 H 21 (CH 3) 2 Si] 3 N, [C 11 H 23 (CH 3 _{) 2 Si] 3 N, [} C 12 H 25 (CH 3) 2 Si] 3 N, [C 13 H 27 (CH 3) 2 Si] 3 N, [C 14 H 29 (CH 3) 2 Si] 3 N, [C ₁₅ H ₃₁ (CH _{3) 2 Si] 3 N,} [C 16 H 33 (CH 3) 2 Si] 3 N, [C 17 H 35 (CH 3) 2 Si] 3 N, [C 18 H 37 (CH 3) 2 Si] ₃ N, [C ₂ F ₅ C ₂ H ₄ (CH ₃ ) ₂ Si] ₃ N, [C ₃ F ₇ C ₂ H ₄ (CH ₃ ) ₂ Si] ₃ N, [C ₄ F ₉ C ₂ H ₄ _{(CH 3) 2 Si] 3} N, [C 5 F 11 C 2 H 4 (CH 3) 2 Si] 3 N, [C 6 F 13 C 2 H 4 (CH 3) 2 Si] 3 N, [C _{7 F 15 C 2 H 4 (} CH 3) 2 Si] 3 N, [C 8 F 17 C 2 H 4 (CH 3) 2 Si] 3 N, C 4 H 9 (CH 3) 2 SiN (CH 3) _{2, C 5 H 11 (CH} 3) 2 SiN (CH 3) 2, C 6 H 13 (CH 3) 2 SiN (CH 3) 2, C 7 H 15 (CH 3) 2 SiN (CH 3) 2, _{C 8 H 17 (CH 3)} 2 SiN (CH 3) 2, C 9 H 19 (CH 3) 2 SiN (CH 3) 2, C 10 H 21 (CH 3) 2 SiN (CH 3) 2, C 11 _{H 23 (CH 3) 2 SiN} (CH 3) 2, C 12 H 25 (CH 3) 2 SiN (CH 3) 2, C 13 H 27 (CH 3) 2 SiN (CH 3) 2, C 14 H 29 _{(CH 3) 2 SiN (CH} 3) 2, C 15 H 31 (CH 3) 2 SiN (CH 3) 2, C 16 H 33 (CH 3) 2 SiN (CH 3) 2, C 17 H 35 (CH _{3) 2 SiN (CH 3)} 2, C 18 H 37 (CH 3) 2 SiN (CH 3) 2, C 5 H 11 (CH 3) HSiN (CH 3) 2, C 6 H 13 (CH 3) HSiN _{(CH 3) 2, C 7} H 15 (CH 3) HSiN (CH 3) 2, C 8 H 17 (CH 3) HSiN (CH 3 _{) 2, C 9 H 19 (} CH 3) HSiN (CH 3) 2, C 10 H 21 (CH 3) HSiN (CH 3) 2, C 11 H 23 (CH 3) HSiN (CH 3) 2, C 12 _{H 25 (CH 3) HSiN (} CH 3) 2, C 13 H 27 (CH 3) HSiN (CH 3) 2, C 14 H 29 (CH 3) HSiN (CH 3) 2, C 15 H 31 (CH 3 _{) HSiN (CH 3) 2,} C 16 H 33 (CH 3) HSiN (CH 3) 2, C 17 H 35 (CH 3) HSiN (CH 3) 2, C 18 H 37 (CH 3) HSiN (CH 3 _{) 2, C 2 F 5 C} 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 3 F 7 C 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 4 F 9 C 2 H _{4 (CH 3) 2 SiN (} CH 3) 2, C 5 F 11 C 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 6 F 13 C 2 H 4 (CH 3) 2 SiN (CH 3 _{) 2, C 7 F 15 C} 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 8 F 17 C 2 H 4 (CH 3) 2 SiN (CH 3) 2, (C 2 H 5) 3 _{SiN (CH 3) 2, C} 3 H 7 (C 2 H 5) 2 SiN (CH 3) 2, C 4 H 9 (C 2 H 5) 2 SiN (CH 3) 2, C 5 H 11 (C 2 _{H 5) 2 SiN (CH 3} ) 2, C 6 H 13 (C 2 H 5) 2 SiN (CH 3) 2, C 7 H 15 (C 2 H 5) 2 SiN (CH 3) 2, C 8 H _{17 (C 2 H 5) 2} SiN (CH 3) 2, C 9 H 19 (C 2 H 5) 2 SiN (CH 3) 2, C 10 H 21 (C 2 H 5) 2 SiN (CH 3) 2 , C ₁₁ H ₂₃ (C ₂ H ₅ ) ₂ SiN (CH ₃ ) ₂ , C ₁₂ H ₂₅ (C _{2 H 5) 2 SiN (CH} 3) 2, C 13 H 27 (C 2 H 5) 2 SiN (CH 3) 2, C 14 H 29 (C 2 H 5) 2 SiN (CH 3) 2, C 15 _{H 31 (C 2 H 5)} 2 SiN (CH 3) 2, C 16 H 33 (C 2 H 5) 2 SiN (CH 3) 2, C 17 H 35 (C 2 H 5) 2 SiN (CH 3) _{2, C 18 H 37 (C} 2 H 5) 2 SiN (CH 3) 2, (C 4 H 9) 3 SiN (CH 3) 2, C 5 H 11 (C 4 H 9) 2 SiN (CH 3) _{2, C 6 H 13 (C} 4 H 9) 2 SiN (CH 3) 2, C 7 H 15 (C 4 H 9) 2 SiN (CH 3) 2, C 8 H 17 (C 4 H 9) 2 SiN _{(CH 3) 2, C 9} H 19 (C 4 H 9) 2 SiN (CH 3) 2, C 10 H 21 (C 4 H 9) 2 SiN (CH 3) 2, C 11 H 23 (C 4 H _{9) 2 SiN (CH 3)} 2, C 12 H 25 (C 4 H 9) 2 SiN (CH 3) 2, C 13 H 27 (C 4 H 9) 2 SiN (CH 3) 2, C 14 H 29 _{(C 4 H 9) 2 SiN} (CH 3) 2, C 15 H 31 (C 4 H 9) 2 SiN (CH 3) 2, C 16 H 33 (C 4 H 9) 2 SiN (CH 3) 2, _{C 17 H 35 (C 4 H} 9) 2 SiN (CH 3) 2, C 18 H 37 (C 4 H 9) 2 SiN (CH 3) 2, C 5 H 11 (CH 3) Si [N (CH 3 _{) 2] 2, C 6 H} 13 (CH 3) Si [N (CH 3) 2] 2, C 7 H 15 (CH 3) Si [N (CH 3) 2] 2, C 8 H 17 (CH 3 _{) Si [N (CH 3)} 2] 2, C 9 H 19 (CH 3) Si [N (CH 3) 2] 2, C 10 H 21 ( _{CH 3) Si [N (CH} 3) 2] 2, C 11 H 23 (CH 3) Si [N (CH 3) 2] 2, C 12 H 25 (CH 3) Si [N (CH 3) 2] _{2, C 13 H 27 (CH} 3) Si [N (CH 3) 2] 2, C 14 H 29 (CH 3) Si [N (CH 3) 2] 2, C 15 H 31 (CH 3) Si [ _{N (CH 3) 2] 2} , C 16 H 33 (CH 3) Si [N (CH 3) 2] 2, C 17 H 35 (CH 3) Si [N (CH 3) 2] 2, C 18 H _{37 (CH 3) Si [N} (CH 3) 2] 2, C 3 F 7 C 2 H 4 (CH 3) Si [N (CH 3) 2] 2, C 4 F 9 C 2 H 4 (CH 3 _{) Si [N (CH 3)} 2] 2, C 5 F 11 C 2 H 4 (CH 3) Si [N (CH 3) 2] 2, C 6 F 13 C 2 H 4 (CH 3) Si [N _{(CH 3) 2] 2,} C 7 F 15 C 2 H 4 (CH 3) Si [N (CH 3) 2] 2, C 8 F 17 C 2 H 4 (CH 3) Si [N (CH 3) _{2] 2, C 6 H 13} Si [N (CH 3) 2] 3, C 7 H 15 Si [N (CH 3) 2] 3, C 8 H 17 Si [N (CH 3) 2] 3, C _{9 H 19 Si [N (CH} 3) 2] 3, C 10 H 21 Si [N (CH 3) 2] 3, C 11 H 23 Si [N (CH 3) 2] 3, C 12 H 25 Si [ _{N (CH 3) 2] 3} , C 13 H 27 Si [N (CH 3) 2] 3, C 14 H 29 Si [N (CH 3) 2] 3, C 15 H 31 Si [N (CH 3) _{2] 3, C 16 H 33} Si [N (CH 3) 2] 3, C 17 H 35 Si [N (CH 3) 2] 3, C 18 H 37 Si [N (CH 3) 2] 3, C ₄ F ₉ C ₂ H ₄ Si [N (CH ₃ ) ₂ _{] 3, C 5 F 11 C} 2 H 4 Si [N (CH 3) 2] 3, C 6 F 13 C 2 H 4 Si [N (CH 3) 2] 3, C 7 F 15 C 2 H 4 Si _{[N (CH 3) 2]} 3, C 8 F 17 C 2 H 4 Si [N (CH 3) 2] 3, C 4 H 9 (CH 3) 2 SiN (C 2 H 5) 2, C 5 H _{11 (CH 3) 2 SiN (} C 2 H 5) 2, C 6 H 13 (CH 3) 2 SiN (C 2 H 5) 2, C 7 H 15 (CH 3) 2 SiN (C 2 H 5) 2 _{, C 8 H 17 (CH 3} ) 2 SiN (C 2 H 5) 2, C 9 H 19 (CH 3) 2 SiN (C 2 H 5) 2, C 10 H 21 (CH 3) 2 SiN (C 2 _{H 5) 2, C 11 H} 23 (CH 3) 2 SiN (C 2 H 5) 2, C 12 H 25 (CH 3) 2 SiN (C 2 H 5) 2, C 13 H 27 (CH 3) 2 _{SiN (C 2 H 5) 2} , C 14 H 29 (CH 3) 2 SiN (C 2 H 5) 2, C 15 H 31 (CH 3) 2 SiN (C 2 H 5) 2, C 16 H 33 ( _{CH 3) 2 SiN (C 2} H 5) 2, C 17 H 35 (CH 3) 2 SiN (C 2 H 5) 2, C 18 H 37 (CH 3) 2 SiN (C 2 H 5) 2, C ₂ F ₅ C ₂ H ₄ (CH ₃ ) ₂ SiN (C ₂ H ₅ ) ₂ , C ₃ F ₇ C ₂ H ₄ (CH ₃ ) ₂ SiN (C ₂ H ₅ ) ₂ , C ₄ F ₉ C ₂ H _{4 (CH 3) 2 SiN (} C 2 H 5) 2, C 5 F 11 C 2 H 4 (CH 3) 2 SiN (C 2 H 5) 2, C 6 F 13 C 2 H 4 (CH 3) 2 SiN (C ₂ H ₅ ) ₂ , C ₇ F ₁₅ C ₂ H ₄ (CH ₃ ) ₂ SiN (C ₂ H ₅ ) ₂ , C ₈ F ₁₇ C ₂ H ₄ _{(CH 3) 2 SiN (C} 2 H 5) 2, (C 2 H 5) 3 SiN (C 2 H 5) 2, C 3 H 7 (C 2 H 5) 2 SiN (C 2 H 5) 2, _{C 4 H 9 (C 2 H} 5) 2 SiN (C 2 H 5) 2, C 5 H 11 (C 2 H 5) 2 SiN (C 2 H 5) 2, C 6 H 13 (C 2 H 5) _{2 SiN (C 2 H 5)} 2, C 7 H 15 (C 2 H 5) 2 SiN (C 2 H 5) 2, C 8 H 17 (C 2 H 5) 2 SiN (C 2 H 5) 2, _{C 9 H 19 (C 2 H} 5) 2 SiN (C 2 H 5) 2, C 10 H 21 (C 2 H 5) 2 SiN (C 2 H 5) 2, C 11 H 23 (C 2 H 5) _{2 SiN (C 2 H 5)} 2, C 12 H 25 (C 2 H 5) 2 SiN (C 2 H 5) 2, C 13 H 27 (C 2 H 5) 2 SiN (C 2 H 5) 2, _{C 14 H 29 (C 2 H} 5) 2 SiN (C 2 H 5) 2, C 15 H 31 (C 2 H 5) 2 SiN (C 2 H 5) 2, C 16 H 33 (C 2 H 5) _{2 SiN (C 2 H 5)} 2, C 17 H 35 (C 2 H 5) 2 SiN (C 2 H 5) 2, C 18 H 37 (C 2 H 5) 2 SiN (C 2 H 5) 2, _{(C 4 H 9) 3 SiN} (C 2 H 5) 2, C 5 H 11 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 6 H 13 (C 4 H 9) 2 SiN (C _{2 H 5) 2, C 7} H 15 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 8 H 17 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 9 H 19 _{(C 4 H 9) 2 SiN} (C 2 H 5) 2, C 10 H 21 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 11 H 23 (C 4 H 9) _{2 SiN (C 2 H 5)} 2, C 12 H 25 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 13 H 27 (C 4 H 9) 2 SiN (C 2 H 5) 2, _{C 14 H 29 (C 4 H} 9) 2 SiN (C 2 H 5) 2, C 15 H 31 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 16 H 33 (C 4 H 9) _{2 SiN (C 2 H 5)} 2, C 17 H 35 (C 4 H 9) 2 SiN (C 2 H 5) 2, C 18 H 37 (C 4 H 9) 2 SiN (C 2 H 5) 2 , etc. Of aminosilane compounds.

Also, the monovalent functional group having an element bonded to the silicon element represented by X in the general formula II-1 is nitrogen may be any one of carbon, hydrogen, boron, nitrogen, phosphorus, oxygen, sulfur, silicon, germanium, fluorine, chlorine, bromine, iodine and the surface functional groups consisting of an element, for example -NHSi (CH _{3) 3} _{group, -NHSi (CH 3) 2 C} 4 H 9 _{group, -NHSi (CH 3) 2 C} 8 H 17 group, -N ( CH ₃₎ ₂ _{groups, -N (C 2 H 5)} 2 _{groups, -N (C 3 H 7)} 2 _{groups, -N (CH 3) (C} 2 H 5) groups, -NH (C ₂ H ₅₎ An -NCO group, an imidazole group, and an acetamide group.

Further, the monovalent functional group whose oxygen atom is bonded to the silicon element represented by X in the general formula II-1 is oxygen may be replaced with carbon, hydrogen, boron, nitrogen, phosphorus, oxygen, sulfur, silicon, germanium, fluorine, chlorine, bromine, iodine and when the functional group consisting of the elements, for example, a group -OCH _3, -OC ₂ H ₅ group, -OC ₃ H ₇ group, -OCOCH ₃ group, -OCOCF _3, and so on.

The halogen group represented by X in the general formula II-1 includes -F, -Cl, -Br, -I, and the like. Among them, a -Cl group is more preferable.

When a is 1 or 2, a in the general formula II-1 is a water surface of 1 to 3. When a surface treatment agent for silicon nitride-containing wafers is stored for a long period of time, polymerization of the silicon compound occurs due to incorporation of moisture, There is a possibility that the storage period becomes short. Further, when the above-mentioned treatment agent is dissolved in a diluting solvent to prepare a surface treatment solution for silicon wafer-containing wafers as described later, water in the atmosphere is mixed in the treatment solution, so that polymerization of the silicon compound occurs, There is a possibility of precipitation. It is preferable that a in the general formula II-1 is 3 (that is, the silicon compound represented by the general formula II-2) in consideration of the time of use of the treating agent and the treating liquid and the cleanliness of the wafer surface after the treatment.

In the silicon compound represented by the general formula (II-1), it is preferable that R ¹ is a hydrocarbon group having 4 to 18 carbon atoms which is unsubstituted or has one hydrocarbon group which may be substituted with a halogen atom and 2 methyl groups Is preferred because the reaction rate with the hydroxyl group on the surface of the wafer is fast. This is because the steric hindrance caused by the hydrophobic group greatly affects the reaction rate in the reaction of the hydroxyl group on the wafer surface with the silicon compound, and the alkyl chain bonded to the silicon element is preferably the shorter one except for the longest one .

From these facts, preferred compounds among the silicon compounds represented by the above-mentioned general formula II-1 include C ₄ H ₉ (CH ₃ ) ₂ SiCl, C ₅ H ₁₁ (CH ₃ ) ₂ SiCl, C ₆ H ₁₃ _{CH 3) 2 SiCl, C 7} H 15 (CH 3) 2 SiCl, C 8 H 17 (CH 3) 2 SiCl, C 9 H 19 (CH 3) 2 SiCl, C 10 H 21 (CH 3) 2 SiCl, _{C 11 H 23 (CH 3)} 2 SiCl, C 12 H 25 (CH 3) 2 SiCl, C 13 H 27 (CH 3) 2 SiCl, C 14 H 29 (CH 3) 2 SiCl, C 15 H 31 (CH _{3) 2 SiCl, C 16 H} 33 (CH 3) 2 SiCl, C 17 H 35 (CH 3) 2 SiCl, C 18 H 37 (CH 3) 2 SiCl, C 2 F 5 C 2 H 4 (CH 3) _{2 SiCl, C 3 F 7 C} 2 H 4 (CH 3) 2 SiCl, C 4 F 9 C 2 H 4 (CH 3) 2 SiCl, C 5 F 11 C 2 H 4 (CH 3) 2 SiCl, C 6 _{F 13 C 2 H 4 (CH} 3) 2 SiCl, C 7 F 15 C 2 H 4 (CH 3) 2 SiCl, C 8 F 17 C 2 H 4 (CH 3) 2 SiCl, C 4 H 9 (CH 3 _{) 2 SiN (CH 3) 2} , C 5 H 11 (CH 3) 2 SiN (CH 3) 2, C 6 H 13 (CH 3) 2 SiN (CH 3) 2, C 7 H 15 (CH 3) 2 _{SiN (CH 3) 2, C} 8 H 17 (CH 3) 2 SiN (CH 3) 2, C 9 H 19 (CH 3) 2 SiN (CH 3) 2, C 10 H 21 (CH 3) 2 SiN ( CH ₃ ) ₂ , C ₁₁ _{H 23 (CH 3) 2 SiN} (CH 3) 2, C 12 H 25 (CH 3) 2 SiN (CH 3) 2, C 13 H 27 (CH 3) 2 SiN (CH 3) 2, C 14 H 29 _{(CH 3) 2 SiN (CH} 3) 2, C 15 H 31 (CH 3) 2 SiN (CH 3) 2, C 16 H 33 (CH 3) 2 SiN (CH 3) 2, C 17 H 35 (CH _{3) 2 SiN (CH 3)} 2, C 18 H 37 (CH 3) 2 SiN (CH 3) 2, C 2 F 5 C 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 3 F 7 _{C 2 H 4 (CH 3)} 2 SiN (CH 3) 2, C 4 F 9 C 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 5 F 11 C 2 H 4 (CH 3) 2 SiN _{(CH 3) 2, C 6} F 13 C 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 7 F 15 C 2 H 4 (CH 3) 2 SiN (CH 3) 2, C 8 F 17 C ₂ H ₄ (CH ₃ ) ₂ SiN (CH ₃ ) ₂ , and the like.

Further, if the surface treatment agent for silicon nitride-containing wafers is a silicon compound represented by the above-mentioned general formula II-4, it is possible to impart better hydrophobicity to the surface of silicon nitride-containing wafers, and as a result, sufficient hydrophobicity can be imparted by a shorter- desirable.

The surface treatment liquid for silicon nitride-containing wafers of the present invention may contain at least the above-mentioned surface treatment agent for silicon nitride-containing wafers, and may contain two or more kinds of the above treatment agents. The treatment agent is dissolved in a diluting solvent. The diluting solvent is not particularly limited as long as it dissolves the above-mentioned treating agent. Examples of the diluting solvent include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, lactone solvents, carbonate solvents, alcohols and derivatives of polyhydric alcohols , A nitrogen-containing solvent, and the like are suitably used. When water is used as a diluting solvent, the reactive sites (X in general formula II-1 or Y in general formula II-2) of the silicon compound, which is a treating agent in the treatment liquid, are hydrolyzed by water to give silanol groups (Si- May be generated. Since the reactive site also reacts with the silanol group, there is a possibility that silicon compounds are bonded to each other to form a dimer. Since the reactivity of the dimer with the hydroxyl group on the surface of the wafer is low, there is a possibility that the time required for hydrophobizing the surface of the wafer is prolonged. Therefore, it is not preferable to use water as a diluting solvent.

In addition, since the silicon compound is easily reacted with the protonic solvent, the use of an aprotic solvent as the organic solvent is particularly preferable because hydrophobicity is easily exhibited in a short time. The aprotic solvent refers to both aprotic polar solvent and aprotic non-polar solvent. Examples of the aprotic solvent include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, lactone-based solvents, carbonate-based solvents, derivatives of polyhydric alcohols not having a hydroxyl group, Containing solvent. Examples of the hydrocarbons include toluene, benzene, xylene, hexane, heptane, and octane. Examples of the esters include ethyl acetate, propyl acetate, butyl acetate, and ethyl acetate. Examples of the ethers include diethyl ether, Examples of the ketones include acetone, acetyl acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, and the like. The halogen-containing solvent For example, perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene and the like, 1,1,1,3,3-pentafluorobutane, Hydrofluorocarbons such as octafluorocyclopentane, 2,3-dihydrodecafluoropentane and Aurora H (manufactured by Japan Zeon Co., Ltd.), hydrofluorocarbons such as methyl perfluoroisobutyl (Manufactured by Asahi Glass Co., Ltd.), Novec7100, Novec7200, Novec7300, and Novec7600 (all manufactured by 3M), and the like, which are commercially available from Asahi Glass Co., Ltd., etc. Chlorocarbon such as tetrachloromethane, hydrochlorocarbon such as chloroform, chlorofluorocarbon such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3,3-penta Fluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2- , 3-trifluoropropene and the like, perfluoroether, and perfluoropolyether. Examples of the sulfoxide-based solvent include dimethylsulfoxide and the like. Examples of the lactone-based solvent include gamma -butyrolactone, gamma -valerolactone, gamma -caprolactone, gamma -heptanolactone ,? -octanoactone,? -octanoactone,? -octanoactone,? -octanolactone,? -octanolactone,? -octanolactone,? -octanolactone,? -octanolactone, There may be mentioned, for example, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, and the like as the carbonate-based solvent. Examples of the carbonate- And examples of the polyhydric alcohol derivative having no hydroxyl group include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene Recolyl 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 Triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol diacetate, tetraethylene glycol monoethyl ether acetate, triethylene glycol monoethyl ether acetate, Ethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol moiety Propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, Butyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl Ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol Triethylene glycol monoethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monoethyl 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, and glycerin triacetate. Examples of the nitrogen element-containing solvent having no NH bond include N, N-dimethylformamide, N, Amide, N-methyl-2-pyrrolidone, triethylamine, pyridine and the like.

If a part or all of the diluting solvent is nonflammable, it is preferable that the treatment liquid becomes incombustible or the flash point becomes high and the risk of the treatment liquid lowers. Since halogen-containing solvents are often non-flammable, non-flammable halogen-containing solvents can be suitably used as nonflammable diluting solvents. In addition, according to the "International Harmonization System for Classification and Labeling of Chemicals: GHS", a solvent whose flash point is 93 ° C or less is defined as a "flammable liquid". Therefore, even if the solvent is not a nonflammable solvent, if a solvent having a flash point exceeding 93 ° C. is used as the diluting solvent, the flash point of the treatment liquid tends to be 93 ° C. or higher and the treatment liquid is less likely to be a "flammable liquid" .

In addition, lactone-based solvents, carbonate-based solvents and derivatives of polyhydric alcohols often have a high flash point, and thus it is preferable to use them as a solvent because the risk of the treatment liquid can be reduced. Specifically, from the above safety standpoint, there may be mentioned γ-butyrolactone, γ-caprolactone, γ-heptanolactone, γ-octanolactone, γ-nonanolactone, γ-decanolactone, γ -Undecanolactone,? -Dodecanolactone,? -Valerolactone,? -Caprolactone,? -Octanol,? -Nonanolactone,? -Decanolactone,? -Undecanolactone,? -Dodecanol Propylene carbonate, ethylene glycol diacetate, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol isomonobutyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether , Diethylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol Triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monomethyl ether, Ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol mono Butyl ether, 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 diacetate, dipropylene glycol diacetate, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol Monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tri Propylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol monomethyl ether acetate, It is more preferable to use, as the solvent, phenol glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, and glycerin triacetate.

The silicon compound is preferably mixed in an amount of 0.1 to 50% by mass based on 100% by mass of the total amount of the treatment liquid, more preferably 0.3 to 20% by mass based on 100% by mass of the total amount of the treatment liquid. If the amount of the silicon compound is less than 0.1% by mass, it may be inactivated by reacting with water or the like contained in a very small amount in the diluting solvent, so that the ability to hydrophobize is insufficient and the surface of the wafer may not be sufficiently hydrophobic. On the other hand, if it is more than 50% by mass, there is a fear of remaining as impurities on the surface of the wafer.

In addition, if the treatment liquid contains an acid, the surface of the silicon nitride-containing wafer can be imparted with sufficient hydrophobicity in a shorter time, which is preferable.

When the silicon compound is a silicon compound represented by the following general formula II-5 in the surface treatment liquid for silicon nitride-containing wafers containing the above-mentioned acid, the surface of the silicon nitride-containing wafer can be imparted with sufficient hydrophobicity by a shorter- Do.

[Formula II-5]

Further, the acid accelerates the reaction between the silicon compound and the hydroxyl group on the silicon nitride-containing wafer surface. As such an acid, it is possible to use an acid such as trifluoroacetic acid, trifluoroacetic acid anhydride, pentafluoropropionic acid, pentafluoropropionic anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, sulfuric acid, You can pick up mountains. Particularly, considering the promoting effect of the reaction, acids such as trifluoroacetic acid, trifluoroacetic acid anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic acid anhydride, sulfuric acid and hydrogen chloride are preferable, and the acid includes water .

The addition amount of the acid is preferably 0.01 to 100% by mass based on 100% by mass of the total amount of the silicon compound. If the addition amount is decreased, the catalytic effect is lowered, which is not preferable. In addition, the catalytic effect is not improved even when added in excess, and when the amount is larger than that of the silicon compound, the catalytic effect may be lowered in some cases. There is also a possibility that it remains on the wafer surface as an impurity. Therefore, the amount of the acid added is preferably 0.01 to 100 mass%, more preferably 0.1 to 50 mass%, based on 100 mass% of the total amount of the silicon compound.

In addition to the above-mentioned acids, the reaction of the silicon compound with the hydroxyl groups on the surface of silicon nitride-containing wafers is promoted, and the treatment solution may contain ammonia, alkylamines, N, N, N ', N'-tetramethylethylenediamine, A base such as aniline, pyridine, piperazine or N-alkylmorpholine, a salt such as ammonium sulfide, potassium acetate or methylhydroxyamine hydrochloride, or a metal complex or metal salt such as tin, aluminum or titanium.

When the carbon number of R ⁴ in the general formula II-5 is 6 to 18, it is more preferable because it can give more excellent hydrophobicity to the silicon nitride-containing wafer surface.

Further, when Z in formula II-5 is a monovalent functional group whose element is bonded to a silicon element, the reaction rate tends to be high, and as a result, it is preferable to exhibit excellent hydrophobicity on the surface of a silicon nitride-containing wafer in a short period of time . The silicon compound, in which Z is a monovalent functional group whose element is bonded to the silicon element, is likely to be inactivated by a by-produced compound due to reaction with the surface of the wafer or reaction with water. On the other hand, in the case where the Z is a silicon compound which is a monovalent functional group whose element bonding with the silicon element is nitrogen, such inactivation is hard to occur.

In the silicon compound having a large number of carbon atoms in the hydrophobic group R ^{1 in} the general formula II-1, the reactivity with the hydroxyl group on the silicon nitride-containing wafer surface may be lowered due to steric hindrance of R ¹ . In this case, by using a silicon compound which is a monovalent functional group whose reactive element X of the general formula (II-1) is a nitrogen-bonded element with a silicon element and by adding an acid not containing water, the hydroxyl group of the silicon nitride- Since the reaction of the silicon compound is promoted to help decrease the reactivity due to the steric hindrance caused by the hydrophobic group.

In the case of the treatment liquid containing the acid, the treatment liquid may be a one-liquid type in which the silicon compound and the acid are mixed from the beginning, or a two-liquid type liquid containing the liquid containing the silicon compound and the acid May be mixed with each other.

Next, the surface treatment method of the wafer of the present invention will be described. The wafer containing silicon nitride subjected to the surface treatment using the treatment agent and treatment liquid of the present invention may be a silicon wafer or a silicon wafer on which a silicon nitride film is formed by a CVD method, a sputtering method or the like. Further, a silicon nitride film may be formed on a wafer not including a silicon element such as a sapphire wafer, various compound semiconductor wafers, and plastic wafers. Further, the treatment liquid can hydrophobicize the surface of the wafer including silicon nitride, the surface of the silicon nitride formed on the wafer, and the like.

Generally, in a wafer having a large number of silicon nitride films or silicon nitride portions on its surface, it is difficult to impart hydrophobicity to the wafer due to a small number of hydroxyl groups on the surface thereof. However, even with such a wafer, the use of the treatment agent and treatment liquid of the present invention can impart sufficient hydrophobicity to the surface of the wafer, and furthermore, has an effect of enhancing adhesion of the wafer surface and the resist. Thus, wafers having a large number of silicon nitride films or silicon nitride parts on the surface are suitable for applying the treatment liquid of the present invention. Further, the surface of the silicon nitride-containing wafer may be cleaned before the surface treatment method of the present invention is performed. Examples of the cleaning liquid used for the cleaning include water, an organic solvent, a mixture of water and an organic solvent, and an acid or base dissolved in them. The silicon nitride-containing wafer may be immersed in the cleaning liquid as the cleaning, or may be subjected to a spin treatment to clean the wafers one by one by supplying the cleaning liquid near the center of rotation while rotating and holding the silicon nitride-containing wafer substantially horizontally. The cleaning liquid may be used in a heated state.

The present invention relates to a method for surface treatment of a wafer which increases the adhesion between the wafer and the resist by hydrophobizing the surface of the wafer containing silicon nitride,

A resist film forming step of forming a resist on the wafer surface

Respectively.

First, in the surface treatment step, the surface of the wafer is brought into contact with the surface treatment agent for silicon nitride-containing wafers or the surface treatment solution for silicon nitride-containing wafers, or the surface of the wafer is brought into contact with a surface treatment agent for silicon nitride containing wafers or a surface treatment solution for silicon nitride- The wafer surface is hydrophobicized. As a method for surface-treating the wafer, a gas obtained by bubbling the treatment agent or the treatment liquid with a gas such as nitrogen is sprayed on the surface of the wafer, or the treatment agent or the treatment solution is vaporized under reduced pressure and / A vapor treatment method is generally used. However, the vapor treatment method is not limited to the vapor treatment method, and may be treated by a liquid treatment method in which the treatment agent or treatment liquid is directly brought into contact with the surface of the wafer. The liquid treatment method can be continuously performed from the surface treatment step to the resist film formation step, for example, by spinning treatment, which leads to a simplification of the production process. It is considered that the surface treatment agent for silicon nitride-containing wafers or the surface treatment liquid for silicon nitride-containing wafers of the present invention has a great advantage because it can impart sufficient hydrophobicity to the silicon nitride-containing wafer surface even by the liquid treatment method.

When the surface treatment agent or the surface treatment liquid is used for the surface treatment by the liquid treatment method, the method of supplying the surface treatment agent or the surface treatment liquid is not particularly limited and the method of contacting the surface of the wafer with the surface treatment agent or the surface treatment liquid It is possible to perform the surface treatment. For example, a spin treatment or the like for processing the wafers one by one by supplying the treatment agent or the treatment liquid near the rotation center while keeping the wafer almost horizontally rotated is more suitably used.

In the surface treatment step, if the temperature of the treatment agent or the treatment liquid is raised, the surface treatment becomes easier in a shorter time. However, if the temperature is excessively high, the stability of the treating agent or the treating solution may be impaired by boiling or evaporating the treating agent or the treating solution. Therefore, the temperature is preferably 10 to 160 ° C, more preferably 15 to 120 ° C desirable.

A resist film forming step of forming a resist film on the surface of the wafer after the surface treatment step is performed. Further, after the surface treatment step, the resist before curing may be supplied to the surface of the wafer in a state in which the treatment agent or the treatment liquid remains, and the treatment agent or the treatment solution may be replaced with the resist. After the treatment agent or treatment liquid is dried, a resist before curing may be supplied to its surface. Further, the surface of the wafer after the surface treatment process may be washed with a solvent or water to remove particles, etc., and a resist before curing may be supplied to the surface of the wafer in a state where the solvent or water remains on the surface of the wafer to replace the solvent or water with the resist After the solvent or water remaining on the surface of the wafer after cleaning is dried, the resist before curing may be supplied to the surface of the wafer. The film formation method of the resist is not particularly limited, and a known method can be used. For example, a spin treatment in which wafers are processed horizontally while rotating the wafers one by one by supplying a resist before curing near the center of rotation while rotating the wafers is more suitably used.

As a general method for forming a fine pattern on the wafer surface through lithography, etching, or the like after film formation of the resist, a resist is applied on the surface of the wafer in the resist film forming step, the resist is exposed through a resist mask, The resist or unexposed resist is removed by etching to prepare a resist having a desired pattern. A resist having a pattern can also be obtained by pressing a mold having a pattern on the resist. Subsequently, the wafer is etched. At this time, concave portions of the resist pattern are selectively etched. Finally, when the resist is peeled off, a wafer having a pattern is obtained.

Example

&Lt; Embodiment of the present invention from the first aspect &

The degree of hydrophobicity of the surface of the wafer and the adhesion between the resist and the wafer have been studied so far and it is known that the higher the hydrophobicity of the wafer surface, the better the adhesion. Thus, the surface of the wafer including the silicon element was treated using the treatment liquid of the present invention, and the contact angle of the treated wafer surface with water was measured to evaluate the hydrophobicity of the treated wafer surface. In addition, in Examples and Comparative Examples, a silicon wafer having a smooth silicon oxide film as a wafer including a silicon element, a silicon wafer having a thermally oxidized film layer having a thickness of 1 mu m on its surface (hereinafter simply referred to as " silicon wafer with silicon oxide film " A silicon wafer having a silicon nitride film with a thickness of 50 nm (hereinafter, simply referred to as a silicon wafer with a silicon nitride film) may be used as the silicon wafer Respectively.

[Evaluation method of contact angle]

About 2 μl of pure water was placed on the surface of the wafer, and the angle between the droplet and the surface of the wafer was measured with a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., CA-X type).

[Example I-1]

(1) Preparation of surface treatment liquid

3 g of hexamethyldisilazane [(CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ ] as a silicon compound, 0.3 g of trifluoroacetic anhydride [(CF ₃ CO) ₂ O] as an acid and 0.3 g of propylene glycol And 96.7 g of monomethyl ether acetate (PGMEA) were mixed and stirred for about 5 minutes to obtain a surface treatment solution having a concentration of silicon compound (hereinafter referred to as " silicon compound concentration ") of 3% by weight based on the total amount of the surface treatment solution .

(2) Cleaning of wafers

A silicon wafer with a silicon oxide film was immersed in a 1 mass% aqueous solution of hydrofluoric acid at room temperature for 2 minutes, then immersed in pure water at room temperature for 1 minute, and then immersed in 2-propanol at room temperature for 1 minute. Further, a silicon wafer with a silicon nitride film was immersed in a 1 mass% aqueous solution of hydrofluoric acid at room temperature for 2 minutes, then immersed in pure water for 1 minute at room temperature, and then 28 mass% ammonia water: 30 mass% hydrogen peroxide: 5, and the mixture was immersed in a washing liquid having a liquid temperature of 70 캜 for 1 minute, dipped in pure water for 1 minute at room temperature, and then immersed in 2-propanol for 1 minute at room temperature.

(3) Surface treatment to the wafer surface Treatment with the surface treatment liquid

A silicon wafer with a silicon oxide film and a silicon wafer with a silicon nitride film after "(2) cleaning of wafers" were respectively immersed in the surface treatment solutions prepared in the above "(1) Preparation of surface treatment solutions" at 20 ° C for 1 minute. Thereafter, the wafer was immersed in 2-propanol at room temperature for 1 minute, and then immersed in pure water at room temperature for 1 minute. Finally, the wafer was taken out of pure water and sprayed with air to remove pure water from the surface.

As shown in Table 1, the initial contact angle before the surface treatment of the silicon wafer with the silicon oxide film was less than 10 deg., And the contact angle after the surface treatment Was 88 °, indicating excellent hydrophobicity. In the case of a silicon wafer with a silicon nitride film, the initial contact angle before the surface treatment was less than 10 °, and the contact angle after the surface treatment was 58 °, indicating hydrophobicity.

[Examples I-2 to I-3]

The silicon compound used in Example I-1 and an acid were appropriately changed to perform surface treatment of the wafer, and the evaluation was carried out. The results are shown in Table 1. (CH ₃ ) ₃ SiN (CH ₃ ) ₂ is trimethylsilyldimethylamine, [CF ₃ (CH ₂ ) ₂ (CH ₃ ) ₂ Si] ₂ NH is bistrifluoropropyldimethylsilazane, CF ₃ COOH is tri Fluoroacetic acid.

[Example I-4]

1 g of butyldimethylsilyldimethylamine [C ₄ H ₉ (CH ₃ ) ₂ SiN (CH ₃ ) ₂ ] as a silicon compound, 0.1 g of trifluoroacetic acid [CF ₃ COOH] as an acid and PGMEA as a diluting solvent; 98.9 g were mixed and stirred for about 5 minutes to prepare a surface treatment solution. The immersion time of each wafer in the surface treatment solution was set to 10 minutes. All other components are the same as in Example I-1. As shown in Table 1, the contact angle after the surface treatment was 87 占 and the hydrophobic property was excellent. The evaluation results of silicon wafers with a silicon nitride film also showed excellent hydrophobicity as shown in Table 1, since the contact angle after the surface treatment was 71 °.

[Examples I-5 to I-25]

The concentration of the silicon compound, the concentration of the silicon compound, the concentration of the acid, the concentration of the acid, the diluting solvent, the immersion time of each wafer in the surface treatment liquid, and the immersion temperature of each wafer in the surface treatment liquid were changed, And the evaluation was carried out. The results are shown in Table 1. In Table 1, C ₈ H ₁₇ (CH ₃ ) ₂ SiN (CH ₃ ) ₂ means octyldimethylsilyldimethylamine, Novec7100 / PGMEA means hydrofluoroether (Novec7100 manufactured by 3M) and PGMEA in Novec7100: PGMEA = 90 : 8.9, and CTFP / PGMEA means a solvent in which 1-chloro-3,3,3-trifluoropropene (CTFP) and PGMEA are mixed in a mass ratio of CTFP: PGMEA = 90: 8.9 And DCTFP / PGMEA means a solvent in which cis-1,2-dichloro-3,3,3-trifluoropropene (DCTFP) and PGMEA are mixed in a mass ratio of DCTFP: PGMEA = 90: 8.9.

[Example I-26]

(1) Preparation of surface treatment liquid

The same surface treatment liquid as in Example I-6 was prepared.

(2) Cleaning of wafers

A silicon wafer with a silicon oxide film and a silicon wafer with a silicon nitride film were cleaned in the same manner as in Example I-1.

(1) The surface treatment liquid (1) was prepared by rotating the spin chuck at a rotation speed of about 100 rpm while holding the wafer after "(2) cleaning of the wafer" Was supplied at 20 占 폚 for 60 seconds and spin-treated. Thereafter, 2-propanol was fed for 1 minute at room temperature to the same rotated wafer, and then pure water was fed at room temperature for 1 minute. Finally, the wafer was rotated at a rotation speed of about 100 rpm to remove pure water from the wafer surface.

As shown in Table 1, the initial contact angle before the surface treatment of the silicon wafer with the silicon oxide film was less than 10 deg., And the contact angle after the surface treatment Was 101 °, indicating excellent hydrophobicity. In the case of silicon wafers with a silicon nitride film, the initial contact angle before the surface treatment was less than 10 °, and the contact angle after the surface treatment was 85 °, indicating excellent hydrophobicity. Further, if the surface treatment step is performed by the spin treatment as described above, since the treatment liquid removing step of the next step and the subsequent resist film forming step can be performed continuously, the production process is simplified and contributes to the improvement of the throughput.

[Example I-27]

1 g of octylsilyl trisdimethylamine [C ₈ H ₁₇ Si [N (CH ₃ ) ₂ ] ₃ ] as a silicon compound, 0.1 g of trifluoroacetic anhydride [(CF ₃ CO) ₂ O] And 98.9 g of PGMEA were mixed and stirred for about 5 minutes to prepare a surface treatment solution. All other components are the same as in Example I-1. As shown in Table 1, the contact angle of the silicon wafer with the silicon oxide film after the surface treatment was 93 °, showing excellent hydrophobicity. Also, as shown in Table 1, the contact angle of the silicon wafer with a silicon nitride film was 87 ° after the surface treatment, showing excellent hydrophobicity. However, when the treatment liquid was allowed to stand in the atmosphere for 30 minutes, a white solid precipitated as a precipitate in the treatment liquid. It is considered that insoluble matter is generated because the polymerization of the silicon compound proceeds by the incorporation of moisture in the atmosphere in the treatment liquid. In addition, in the examples other than this embodiment, the above-mentioned precipitation of solid did not occur.

[Comparative Example I-1]

3 g of hexamethyldisilazane [(CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ ] as a silicon compound and 97 g of hydrofluoroether (Novec7100 manufactured by 3M) as a diluting solvent were mixed and stirred for about 5 minutes to carry out surface treatment Was prepared. The surface treatment solution was placed in a 500 mL beaker, and placed on a hot plate set at 200 DEG C and boiled. A silicon wafer with a silicon oxide film and a silicon wafer with a silicon nitride film cleaned in the same manner as in "(2) Cleaning of wafers" in Example I-1 were once dried and then subjected to vaporization of the vaporized surface treatment liquid by boiling And the vapor prime method was simply reproduced by exposing the wafer for 5 minutes. The exact temperature of the steam is unknown, but it is thought that the boiling point of Novec7100 is over 61 ℃. The evaluation results of the silicon wafer with a silicon oxide film showed excellent hydrophobicity as shown in Table 1, with a contact angle of 81 deg. After surface treatment, but the energy loss was larger than that of the surface treatment method in which the wafer was brought into contact with the treatment solution. On the other hand, as shown in Table 1, the contact angle of the silicon wafer with silicon nitride film after the surface treatment was 46 deg.

[Comparative Example I-2]

10 g of hexamethyldisilazane [(CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ ] as a silicon compound and 90 g of PGMEA as a diluting solvent were mixed and stirred for about 5 minutes to prepare a surface treatment solution. The immersing time of each wafer in the surface treatment solution was 60 minutes. All other components are the same as in Example I-1. As shown in Table 1, the contact angle of the silicon wafer with silicon oxide film was 63 ° after the surface treatment, showing hydrophobicity. However, in the case of the surface treatment method of bringing the wafer into contact with the treatment liquid, The throughput was bad as needed. Also, as shown in Table 1, the contact angle after the surface treatment was 36 deg., And the hydrophobicity was not sufficient.

In the case of Examples I-1 to I-27 using the treatment liquid containing the acid and the diluting solvent and the silicon compound represented by the general formula I-1 as described above, the surface treatment method for contacting the treatment liquid with the wafer Thereby imparting hydrophobicity to the wafer surface. Further, in the case of Examples I-1 to I-26 using a treatment liquid containing an acid and a diluting solvent and a silicon compound represented by the general formula I-2, hydrophobicity can be imparted to the surface of the wafer, Insoluble matter was not precipitated in the treatment liquid even if it was left in the atmosphere. Further, in Examples I-4 to I-26 using a treating solution containing an acid and a diluting solvent and the silicon compound represented by the above-mentioned general formula I-3, more excellent hydrophobicity could be imparted to the wafer surface. In the case of Examples I-6 to I-26 in which a treatment liquid containing an acid and a diluting solvent and a silicon compound having R < ² > in the general formula I-3 having 6 to 18 carbon atoms was used, .

In addition, the method of surface-treating wafers in the above-mentioned example had less energy loss involved in the surface treatment for hydrophobicity of the surface of the wafer as compared with the conventional steam prime method reproduced in the comparative example I-1. Further, for example, in the spin treatment of the surface of the wafer in Example I-26, since the surface treatment process, the treatment liquid removal process, and the resist film formation process of the present invention can be continuously performed, the throughput is good Respectively.

Further, in Comparative Example I-1, it was possible to impart excellent hydrophobicity to a silicon wafer with a silicon oxide film having a large number of hydroxyl groups per unit area, but it was impossible to impart sufficient hydrophobicity to a silicon wafer with a silicon nitride film having a small number of hydroxyl groups per unit area In the above embodiment, hydrophobicity can be imparted to any of silicon wafers with silicon oxide films and silicon wafers with silicon nitride wafers.

In Comparative Example I-2 containing no acid in the treatment liquid, it was possible to impart hydrophobicity to a silicon wafer with a silicon oxide film having a large amount of hydroxyl groups per unit area, but it required a long time to exhibit hydrophobicity and had poor throughput. Further, sufficient hydrophobicity could not be imparted to a silicon wafer with a silicon nitride film having a small number of hydroxyl groups per unit area.

&Lt; Embodiment of the present invention from the second aspect &

The degree of hydrophobicity of the surface of the wafer and the adhesion between the resist and the wafer have been studied so far and it is known that the higher the hydrophobicity of the wafer surface, the better the adhesion. Thus, the surface of the silicon nitride-containing wafer was treated using the treating agent or treating solution of the present invention, and the contact angle of the treated wafer surface with water was measured to evaluate the hydrophobicity of the treated wafer surface.

[Evaluation method of contact angle]

[Example II-1]

(1) Preparation of surface treatment liquid for silicon nitride-containing wafers

1 g of nonafluorohexyldimethylchlorosilane (C ₄ F ₉ (CH ₂ ) ₂ (CH ₃ ) ₂ SiCl) as a silicon compound, 96 g of hydrofluoroether (Novec7100 manufactured by 3M) as a diluting solvent, 96 g of propylene glycol mono (Hereinafter referred to as Novec7100 / PGMEA-3 in Table 2) and stirred for about 5 minutes to adjust the concentration of the silicon compound to the total amount of the surface treatment solution (hereinafter referred to as " concentration of silicon compound &Quot;) is 1% by mass, is obtained.

(2) Cleaning of silicon nitride-containing wafers

A silicon wafer (smooth silicon wafer having a silicon nitride layer with a thickness of 50 nm on the surface) and a smooth silicon nitride film prepared by LP-CVD was immersed in a 1 mass% aqueous solution of hydrofluoric acid at room temperature for 2 minutes, Minute, and 28% by mass ammonia water: 30% by mass hydrogen peroxide water: water was mixed at a volume ratio of 1: 1: 5, and the mixture was immersed in a washing liquid having a liquid temperature of 70 캜 for 1 minute on a hot plate, And immersed in 2-propanol at room temperature for 1 minute.

(3) Surface treatment of the silicon nitride-containing wafer surface by the treatment liquid

The wafer after "(2) cleaning of silicon nitride-containing wafers" was immersed in the treatment liquid prepared in "(1) Preparation of surface treatment liquid for silicon nitride-containing wafers" at 20 ° C. for 1 minute. Thereafter, the wafer was immersed in 2-propanol at room temperature for 1 minute, and then immersed in pure water at room temperature for 1 minute. Finally, the wafer was taken out of pure water and sprayed with air to remove pure water from the surface.

Each of the obtained wafers was evaluated by the method described in the above-mentioned "evaluation method of contact angle". As shown in Table 2, the initial contact angle before the surface treatment was less than 10 °, the contact angle after the surface treatment was 94 °, .

[Examples II-2 to II-3]

The surface treatment of the wafers was carried out in the same manner as in Example II-1 by appropriately changing the diluting solvent used in Example II-1, and the evaluation was carried out. The results are shown in Table 2. In Table 2, CTFP / PGMEA means a solvent using 1-chloro-3,3,3-trifluoropropene (CTFP) instead of Novec7100 in Example II-1, DCTFP / 1,2-dichloro-3,3,3-trifluoropropene (DCTFP) instead of Novec7100.

[Example II-4]

10 g of octyldimethylchlorosilane [C ₈ H ₁₇ (CH ₃ ) ₂ SiCl] as a silicon compound, 80 g of hydrofluoroether (3M manufactured by Novec 700) as a diluting solvent, 10 g of propylene glycol monomethyl ether acetate (PGMEA) g (the above solvent is represented by Novec7100 / PGMEA-10 in Table 2) and stirred for about 5 minutes to obtain a silicon nitride-containing wafer surface treatment solution having a silicon compound concentration of 10 mass% based on the total amount of the surface treatment solution . Then, the silicon wafer with the silicon nitride film was immersed in the treatment solution at 20 캜 for 60 minutes. The other treatments are the same as in Example II-1. The obtained wafers were evaluated by the method described in the above-mentioned "evaluation method of contact angle". As shown in Table 2, the initial contact angle before the surface treatment was less than 10 °, and the contact angle after the surface treatment was 75 °, .

[Example II-5]

1 g of octyldimethylsilyldimethylamine [C ₈ H ₁₇ (CH ₃ ) ₂ SiN (CH ₃ ) ₂ ] as a silicon compound, 98.9 g of PGMEA as a diluting solvent, and further, trifluoroacetic acid [CF ₃ COOH] Were mixed and stirred for about 5 minutes to obtain a silicon nitride-containing wafer surface treatment solution having a silicon compound concentration of 1 mass%. The addition amount of the acid (hereinafter referred to as the acid concentration) relative to 100 mass% of the silicon compound is 10 mass%. All other components are the same as in Example II-1. As a result of the evaluation, as shown in Table 2, the contact angle after the surface treatment was 86 °, showing excellent hydrophobicity.

[Examples II-6 to II-24, II-27 to II-29]

The surface treatment of the wafers was carried out by appropriately changing the silicon compound, silicon compound concentration, acid, acid concentration, diluting solvent, surface treatment time and surface treatment temperature used in Example II-5, and evaluation thereof was carried out. The results are shown in Table 2. In Table 2, C ₄ H ₉ (CH ₃ ) ₂ SiN (CH ₃ ) ₂ means butyldimethylsilyldimethylamine, and (CF ₃ CO) ₂ O means trifluoroacetic anhydride.

[Example II-25]

Octyl-silyl-tris dimethylamine [C ₈ H ₁₇ Si [N (CH ₃₎ _2] _3] a silicon compound; 1 g, PGMEA as a diluting solvent, acetic anhydride, trifluoroacetic as acid additional 98.9 g, [(CF ₃ CO ) ₂ O) were mixed and stirred for about 5 minutes to obtain a silicon nitride-containing wafer surface treatment solution having a silicon compound concentration of 1 mass%. All other components are the same as in Example II-5. As a result of the evaluation, as shown in Table 2, the contact angle after the surface treatment was 87 °, showing excellent hydrophobicity. However, when the treatment liquid was allowed to stand in the atmosphere for 30 minutes, a white solid precipitated as a precipitate in the treatment liquid. It is considered that insoluble matter is generated because the polymerization of the silicon compound proceeds by the incorporation of moisture in the atmosphere in the treatment liquid. In addition, in the examples other than this embodiment, the above-mentioned precipitation of solid did not occur.

[Example II-26]

A silicon nitride-containing surface treatment liquid for wafers as in Example II-5 was prepared.

(2) Cleaning of silicon nitride-containing wafers

A smooth silicon wafer (smooth silicon wafer having a silicon nitride layer with a thickness of 50 nm on the surface and a diameter of 4 inches) made by LP-CVD was immersed in a 1 mass% aqueous solution of hydrofluoric acid at room temperature for 2 minutes, , And the mixture was immersed in pure water for 1 minute, and 28% by mass ammonia water: 30% by mass hydrogen peroxide water: water was mixed at a volume ratio of 1: 1: 5 and immersed in a washing solution having a liquid temperature of 70 캜 for one minute on a hot plate, For 1 minute and immersed in 2-propanol at room temperature for 1 minute.

Holding the wafer after "(2) cleaning of silicon nitride-containing wafers" almost horizontally and rotating the spin chuck as a wafer holding and rotating mechanism, rotating the spin chuck at a rotation speed of about 100 rpm, Containing wafer for surface treatment "was supplied at 20 캜 for 60 seconds and subjected to spin treatment. Thereafter, 2-propanol was fed for 1 minute at room temperature to the same rotated wafer, and then pure water was fed at room temperature for 1 minute. Finally, the wafer was rotated at a rotation speed of about 100 rpm to remove pure water from the wafer surface.

The obtained wafers were evaluated by the method described in the above-mentioned "evaluation method of contact angle". As shown in Table 2, the initial contact angle before the surface treatment was less than 10 °, and the contact angle after the surface treatment was 85 °, .

[Comparative Example II-1]

10 g of hexamethyldisilazane [HMDS, [(CH ₃ ) ₃ Si] ₂ NH] as a silicon compound and 90 g of propylene glycol monomethyl ether acetate (PGMEA) as a diluting solvent were used to perform surface treatment for silicon nitride- Was prepared. The surface treatment time was set to 60 minutes. All other components are the same as in Example II-1. As shown in Table 2, the contact angle after the surface treatment was 36 占 and the hydrophobicity was low.

[Comparative Example II-2]

3 g of hexamethyldisilazane [HMDS, [(CH ₃ ) ₃ Si] ₂ NH] as a silicon compound, and 97 g of hydrofluoroether (Novec7100 manufactured by 3M) as an organic solvent were used to perform surface treatment for silicon nitride- Was prepared. The silicon nitride-containing wafer having been cleaned in the same manner as in Example II-1 was once dried, placed on a hot plate set at 250 DEG C with the beaker in which the treatment liquid was placed, and the treatment liquid was exposed to steam for 5 minutes And the vapor of the treatment liquid was adhered to the surface of the wafer. The exact temperature of the steam is unknown, but it is considered to be above the boiling point of Novec7100 of 61 ° C. As a result of the evaluation, as shown in Table 2, the contact angle after the surface treatment was 46 占 and the hydrophobicity was low.

[Referential Example II-1]

The procedure of Example II-5 was repeated except that 1 g of trimethylsilyldimethylamine [(CH ₃ ) ₃ SiN (CH ₃ ) ₂ ] was used as a silicon compound. As a result of the evaluation, as shown in Table 2, the contact angle after the surface treatment was 60 °.

[Referential Example II-2]

Except that 1 g of bistrifluoropropyldimethylsilazane [CF ₃ (CH ₂ ) ₂ (CH ₃ ) ₂ Si] ₂ NH] was used as the silicon compound. As a result of the evaluation, as shown in Table 2, the contact angle after the surface treatment was 62 °.

As described above, in Examples II-1 to II-29 using the treatment liquid containing the silicon compound represented by the general formula II-1, hydrophobicity could be imparted to the silicon nitride-containing wafer surface. In Examples II-1 to II-24 and II-26 to II-29 using the treatment liquid containing the silicon compound represented by the general formula II-2, it is possible to impart hydrophobicity to the surface of the silicon nitride- , And even if the treatment solution was left in the atmosphere, insoluble matter was not precipitated in the treatment solution. In Examples II-1 to II-24 and II-26 to II-29 using the treatment liquid containing the silicon compound represented by Formula II-3, hydrophobicity can be imparted to the surface of the wafer in a shorter time there was. Further, in Examples II-1 to II-3 using the treatment liquid containing the silicon compound represented by the general formula II-4, the surface of the wafer could be imparted with better hydrophobicity in a shorter time. In Examples II-5 to II-24 and II-26 to II-28 using the treatment liquid containing the silicon compound represented by Formula II-5, hydrophobicity can be imparted to the surface of the wafer in a shorter time there was. In Examples II-5 to II-24 and II-26 using a treatment liquid containing a silicon compound having 6 to 18 carbon atoms in the R ⁴ of the general formula II-5, the surface of the wafer was imparted with better hydrophobicity Could. In Examples II-5 to II-24 and II-26 in which a treatment liquid containing a silicon compound, which is a monovalent functional group whose element bonding to the silicon element is nitrogen, in the general formula II-5 is used, It was possible to give more excellent hydrophobicity to the polymer. On the contrary, in Comparative Examples II-1 to II-2, it was not possible to impart sufficient hydrophobicity to the silicon nitride-containing wafer surface. In addition, Examples II-1 to II-29 were able to impart better hydrophobicity to Reference Examples II-1 to II-2.

Claims

delete

There is provided a method for surface treatment of a wafer which increases the adhesion between the wafer and the resist by hydrophobizing the surface of the wafer containing the silicon element,
A surface treatment step of bringing a surface treatment liquid for a silicon element-containing wafer into contact with the surface of the wafer to hydrophilize the surface of the wafer,
A process liquid removing step of removing the process liquid from the wafer surface,
A resist film forming step of forming a resist on the wafer surface
Wherein the silicon element-containing wafer is a silicon element-containing wafer characterized in that it comprises a silicon compound, an acid and a diluting solvent represented by the following general formula I-3 in the surface treatment step Surface treatment method of:

In the formula I-3, R ² is a hydrocarbon group having 4 to 18 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom. X is a monovalent functional group whose element bonding to the silicon element is nitrogen.

6. The method of claim 5,
Wherein the surface treatment step comprises spinning the silicon element-containing wafer with the treatment solution, or immersing the silicon element-containing wafer in the treatment solution.

The method according to claim 5 or 6,
The wafer containing the silicon element is:
Silicon wafers;
A wafer on which a silicon oxide film, a silicon nitride film, or a polysilicon film is formed on a silicon wafer;
A wafer on which the surface of the silicon wafer, the surface of the silicon nitride film, or the surface of the polysilicon film is naturally oxidized;
A wafer composed of a plurality of components comprising at least one selected from silicon and silicon oxide;
Silicon carbide wafers;
A wafer on which a film containing a silicon element is formed on a wafer not containing a silicon element
The surface of the silicon element-containing wafer.

A surface treatment agent for silicon nitride-containing wafers for improving adhesion between a wafer and a resist by hydrophobizing the surface of the wafer before depositing a resist on the wafer surface containing silicon nitride, characterized in that the treatment agent is a silicon compound represented by the following general formula Wherein the surface treatment agent is a silicon nitride-containing surface treating agent.

[In the formula (II-3), R ² is a hydrocarbon group having 6 to 8 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom. X is a Cl group.]

9. The method of claim 8,
And R < ² > is a hydrocarbon group in which at least a part of hydrogen atoms are substituted with fluorine atoms.

A surface treatment liquid for a silicon nitride-containing wafer containing a surface treatment agent for a silicon nitride-containing wafer according to any one of claims 8 to 9 and a diluting solvent, wherein the silicon compound is contained in an amount of from 0.1 to 50 mass% with respect to a total amount of 100 mass% And the surface treatment liquid for silicon nitride-containing wafers.

A silicon nitride-containing surface treatment liquid for silicon wafers for improving adhesion between a wafer and a resist by hydrophobizing the surface of the wafer before depositing a resist on the wafer surface containing silicon nitride,
A surface treatment agent for silicon nitride-containing wafers represented by the following general formula (II-3)
Acid, and
A diluting solvent,
Wherein the surface treatment agent is contained in an amount of 0.1 to 50 mass% with respect to a total amount of the treatment liquid of 100 mass%.

[In the formula II-3, R ² is a hydrocarbon group having 4 to 8 carbon atoms, and the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom. And X is a monovalent functional group whose element bonding to the silicon element is nitrogen.]

12. The method of claim 11,
Wherein the carbon number of R < ² > is 6 to 8.

There is provided a wafer surface treatment method for improving the adhesion between a wafer and a resist by hydrophobizing the surface of the wafer containing silicon nitride,
A surface treatment step of contacting the surface of the wafer with steam of a surface treatment agent for silicon nitride containing wafers or contacting the surface of the wafer with a surface treatment agent for silicon nitride containing wafers to hydrophobicize the surface of the wafer,
A resist film forming step of forming a resist on the wafer surface
Wherein the surface treatment agent for silicon nitride-containing wafers according to claim 8 or 9 is used in the surface treatment step.

There is provided a wafer surface treatment method for improving the adhesion between a wafer and a resist by hydrophobizing the surface of the wafer containing silicon nitride,
A surface treatment step of contacting the surface of the wafer with steam of a surface treatment liquid for silicon nitride containing wafers or contacting the surface of the wafer with a surface treatment liquid for silicon nitride containing wafers to hydrophobicize the surface of the wafer,
A resist film forming step of forming a resist on the wafer surface
Wherein the surface treatment liquid for silicon nitride-containing wafers according to claim 10 is used in the surface treatment step.

There is provided a wafer surface treatment method for improving the adhesion between a wafer and a resist by hydrophobizing the surface of the wafer containing silicon nitride,
A surface treatment step of contacting the surface of the wafer with steam of a surface treatment liquid for silicon nitride containing wafers or contacting the surface of the wafer with a surface treatment liquid for silicon nitride containing wafers to hydrophobicize the surface of the wafer,
A resist film forming step of forming a resist on the wafer surface
Wherein the surface treatment liquid for silicon nitride-containing wafers according to claim 11 is used in the surface treatment step.

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