JP5716527B2 - Chemical solution for forming water repellent protective film and method for cleaning wafer using the chemical solution - Google Patents

Description

  The present invention relates to a substrate wafer cleaning technique in semiconductor device manufacturing or the like.

  In the manufacture of semiconductor chips, a fine uneven pattern is formed on the surface of a silicon wafer through film formation, lithography, etching, and the like, and then cleaning is performed using water or an organic solvent to clean the wafer surface. The The elements are in the direction of miniaturization, and the interval between the concave and convex patterns is becoming narrower. For this reason, the problem that the concavo-convex pattern collapses due to the capillary phenomenon when washing with water and drying the water from the wafer surface is likely to occur. This problem has become more prominent particularly in semiconductor chips of the 20 nm and 10 nm generations where the pattern spacing of the unevenness is narrower.

  As a method for cleaning the wafer surface while preventing the pattern from collapsing, Patent Document 1 discloses a method in which water remaining on the wafer surface is replaced with isopropanol and then dried. Patent Document 2 discloses a method in which after a wafer surface is washed with water, a water-repellent protective film is formed on a concavo-convex pattern portion containing silicon, followed by rinsing with water and drying. This protective film is finally removed. Since the pattern portion is rendered water-repellent by the protective film when rinsing with water, the effect of suppressing the collapse of the concavo-convex pattern is produced. This method is said to be effective even for patterns having an aspect ratio of 8 or more.

JP 2003-45843 A Japanese Patent No. 4403202

  In order to prevent pattern collapse by making the surface of the concavo-convex pattern water repellent, in order to form a water-repellent protective film on the concavo-convex pattern surface containing silicon, a hydroxyl group or the like present on the concavo-convex pattern surface or the wafer surface It is necessary to bind the reaction active site of the compound and a compound that forms a protective film. The concavo-convex pattern containing silicon differs in the amount of hydroxyl groups per unit area because the amount of the original hydroxyl groups differs depending on the type and the ease of formation of hydroxyl groups varies depending on the conditions of surface treatment with water or acid. May occur. In the conventional technique, a sufficient water repellent effect cannot be imparted to a substrate with little hydroxyl group formation, and pattern collapse may not be effectively prevented. The present invention relates to a method for cleaning a wafer while preventing a concavo-convex pattern from falling over, and a water-repellent protective film forming agent capable of efficiently cleaning even when the amount of hydroxyl groups on the pattern surface is small, and It is an object of the present invention to provide a chemical solution for forming a water-repellent protective film containing the agent and a method for cleaning a wafer using the chemical solution.

  In the present invention, in order to achieve the above-mentioned problem, a water-repellent protective film-forming chemical solution for forming a water-repellent protective film (hereinafter sometimes simply referred to as “protective film”) on at least the concave surface of the concave-convex pattern Focused on water-repellent protective film forming agent (hereinafter sometimes referred to as “protective film forming agent”) contained in (hereinafter sometimes referred to as “chemical liquid for forming protective film” or simply “chemical liquid”) . That is, the present invention is an agent that can effectively produce water repellency even if a wafer having a concavo-convex pattern containing silicon on the surface has a difference in the ease of formation of hydroxyl groups depending on the concavo-convex pattern or the type of wafer. That is, by forming a protective film with the protective film forming agent contained in the chemical solution, the width of change in the cleaning conditions for each production lot is reduced, and the wafer is cleaned industrially advantageously.

  The present inventors have intensively studied, and by using a chemical solution containing a silicon compound having a specific hydrophobic group as a protective film forming agent, it is difficult to depend on the number of hydroxyl groups present on the uneven pattern surface of the wafer. It was found that a protective film capable of producing good water repellency was formed, and the pattern surface could be cleaned efficiently.

  That is, the invention described in [Invention 1] to [Invention 10] below is provided.

[Invention 1]
A water-repellent protective film forming agent for forming a protective film on at least the concave surface of the wafer when cleaning a wafer having a concave-convex pattern on the surface and containing silicon element on at least the concave surface of the concave-convex pattern, A water repellent protective film-forming agent, which is a silicon compound represented by the following general formula [1].

[Wherein, R ^{1 s} are each independently a hydrogen group or an unsubstituted or halogenated hydrocarbon group having 1 to 18 carbon atoms, and the total carbon number of R ^{1 s} that are independent of each other is 6 or more, and X is each independently a monovalent functional group in which the element bonded to the silicon element is nitrogen, a monovalent functional group in which the element bonded to the silicon element is oxygen, and halogen And at least one group selected from the group, a is an integer of 1 to 3. ]
[Invention 2]
A water-repellent protective film forming agent for forming a protective film on at least the concave surface of the wafer when cleaning a wafer having a concave-convex pattern on the surface and containing silicon nitride on at least the concave surface of the concave-convex pattern, A water repellent protective film-forming agent, which is a silicon compound represented by the following general formula [1].

[Wherein, R ^{1 s} are each independently a hydrogen group or an unsubstituted or halogenated hydrocarbon group having 1 to 18 carbon atoms, and the total carbon number of R ^{1 s} that are independent of each other is 6 or more, and X is each independently a monovalent functional group in which the element bonded to the silicon element is nitrogen, a monovalent functional group in which the element bonded to the silicon element is oxygen, and halogen And at least one group selected from the group, a is an integer of 1 to 3. ]
[Invention 3]
The water repellent protective film forming agent according to invention 1 or invention 2, wherein the silicon compound represented by the general formula [1] is represented by the following general formula [2].

[Wherein R ¹ and X are the same as those in the general formula [1]. ]
[Invention 4]
The water repellent protective film forming agent according to invention 1 or invention 2, wherein the silicon compound represented by the general formula [1] is represented by the following general formula [3].

[Wherein R ² is an unsubstituted or substituted hydrocarbon group having 4 to 18 carbon atoms, and X is the same as in general formula [1]. ]
[Invention 5]
A chemical solution for forming a water-repellent protective film, comprising the water-repellent protective film-forming agent according to any one of Inventions 1 to 4.

[Invention 6]
The chemical solution for forming a water-repellent protective film according to the invention 5, characterized by containing an acid.

[Invention 7]
Invention 5 or invention characterized in that the water repellent protective film forming agent is mixed so that the water repellent protective film forming chemical solution is 0.1 to 50% by mass with respect to 100% by mass of the total amount of the water repellent protective film forming chemical. 6. A chemical solution for forming a water-repellent protective film according to 6.

[Invention 8]
In the cleaning of a wafer containing a silicon element on at least the concave surface of the concavo-convex pattern in the wafer having the concavo-convex pattern formed on the surface, the steps shown below,
Cleaning the wafer surface with an aqueous cleaning liquid, an aqueous cleaning liquid cleaning step;
A water repellent protective film forming step of holding a water repellent protective film forming chemical in at least the concave portion of the wafer and forming a water repellent protective film on the concave surface;
A liquid removal process for removing liquid on the wafer surface;
Removing the water-repellent protective film from the concave surface, a water-repellent protective film removing step,
A method for cleaning a wafer comprising using the chemical solution for forming a water-repellent protective film according to any one of Inventions 5 to 7 in the water-repellent protective film forming step.

[Invention 9]
9. The wafer cleaning method according to claim 8, wherein the wafer is a wafer containing silicon nitride on at least a concave surface of the concave / convex pattern.

[Invention 10]
The water repellent protective film removing step is at least selected from irradiating the wafer surface with light, heating the wafer, irradiating the wafer surface with plasma, exposing the wafer surface to ozone, and corona discharging the wafer. characterized in that it is carried out in one processing method, the wafer cleaning method according to the invention 8 or invention 9.

  By using the water-repellent protective film forming agent of the present invention, a protective film showing good water repellency is formed in the cleaning process of the wafer containing silicon on the concave surface, and the number dependency of the hydroxyl groups present on the concave-convex pattern surface It is effective in reducing By applying the present invention, it is possible to stably clean the wafer while preventing the concavo-convex pattern from collapsing, and it is possible to reduce changes in cleaning conditions according to production lots.

It is a figure which shows a schematic diagram when the wafer 1 by which the surface was made into the surface which has the uneven | corrugated pattern 2 is seen. FIG. 2 shows a part of the a-a ′ cross section in FIG. 1. The recessed part 4 has shown the schematic diagram of the state holding the chemical | medical solution 8 for water-repellent protective film formation. It is a figure which shows the schematic diagram of the state by which the liquid 9 was hold | maintained at the recessed part 4 in which the water-repellent protective film 10 was formed.

Hereinafter, the present invention will be described in more detail. First, the water-repellent protective film-forming agent provided in the present invention has a water-repellent property on at least the concave surface of the wafer when cleaning the wafer containing silicon on at least the concave surface of the concave-convex pattern on the wafer having the concave-convex pattern formed on the surface. It is a water repellent protective film forming agent for forming a protective film, and the agent is a silicon compound represented by the following general formula [1].

[Wherein, R ^{1 s} are each independently a hydrogen group or an unsubstituted or halogenated hydrocarbon group having 1 to 18 carbon atoms, and the total carbon number of R ^{1 s} that are independent of each other is 6 or more, and X is each independently a monovalent functional group in which the element bonded to the silicon element is nitrogen, a monovalent functional group in which the element bonded to the silicon element is oxygen, and halogen And at least one group selected from the group, a is an integer of 1 to 3. ]
The hydrocarbon group represented by R ¹ is a hydrophobic group. When a protective film is formed with a large hydrophobic group, the surface of the wafer after processing exhibits good water repellency. If the total carbon number of R ¹ is 6 or more, a water-repellent film capable of sufficiently producing water-repellent performance can be formed even if the number of hydroxyl groups per unit area of the concavo-convex pattern containing silicon element is small.

  The silicon compound can chemically react with the concavo-convex pattern and the hydroxyl group on the wafer surface. As a result, the silicon element of the silicon compound is chemically bonded to the concavo-convex pattern and the silicon element on the wafer surface, and the water repellency. Since the protective film is formed, the protective film can be held on the wafer surface against washing with water or a solvent after the protective film is formed.

Examples of the silicon compound represented by the general formula [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, and 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 SiC _{, 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, (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 ₂₅ (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 (CH _{3 ) SiCl 2, C 8 H 17} (CH 3) SiCl _{, 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) _{iCl 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, etc. A chlorosilane type compound is mentioned.

Also, for example, C ₄ H ₉ (CH ₃ ) ₂ SiOCH ₃ , C ₅ H ₁₁ (CH ₃ ) ₂ SiOCH ₃ , C ₆ H ₁₃ (CH ₃ ) ₂ SiOCH ₃ , C ₇ H ₁₅ (CH ₃ ) ₂ SiOCH ₃ , C ₈ H ₁₇ (CH ₃ ) ₂ SiOCH ₃ , C ₉ H ₁₉ (CH ₃ ) ₂ SiOCH ₃ , C ₁₀ H ₂₁ (CH ₃ ) ₂ SiOCH ₃ , C ₁₁ H ₂₃ (CH ₃ ) ₂ SiOCH ₃ , _{C 12 H 25 (CH 3)} 2 SiOCH 3, C 13 H 27 (CH 3) 2 SiOCH 3, C 14 H 29 (CH 3) 2 SiOCH 3, C 15 H 31 (CH 3) 2 SiOCH 3, C 16 _{H 33 (CH 3) 2 SiOCH} 3, C 17 H 35 (CH 3) 2 SiOCH 3, C 18 H 37 (CH 3) 2 SiOCH _{, C 5 H 11 (CH 3} ) HSiOCH 3, C 6 H 13 (CH 3) HSiOCH 3, C 7 H 15 (CH 3) HSiOCH 3, C 8 H 17 (CH 3) HSiOCH 3, C 9 H 19 ( CH ₃ ) HSiOCH ₃ , C ₁₀ H ₂₁ (CH ₃ ) HSiOCH ₃ , C ₁₁ H ₂₃ (CH ₃ ) HSiOCH ₃ , C ₁₂ H ₂₅ (CH ₃ ) HSiOCH ₃ , C ₁₃ H ₂₇ (CH ₃ ) HSiOCH ₃ , _{C 14 H 29 (CH 3)} HSiOCH 3, C 15 H 31 (CH 3) HSiOCH 3, C 16 H 33 (CH 3) HSiOCH 3, C 17 H 35 (CH 3) HSiOCH 3, C 18 H 37 (CH _{3) HSiOCH 3, C 2 F} 5 C 2 H 4 (CH 3) 2 SiOCH 3, C 3 F 7 C 2 _{H 4 (CH 3) 2 SiOCH} 3, C 4 F 9 C 2 H 4 (CH 3) 2 SiOCH 3, C 5 F 11 C 2 H 4 (CH 3) 2 SiOCH 3, C 6 F 13 C 2 H 4 (CH ₃ ) ₂ SiOCH ₃ , C ₇ F ₁₅ C ₂ H ₄ (CH ₃ ) ₂ SiOCH ₃ , C ₈ F ₁₇ C ₂ H ₄ (CH ₃ ) ₂ SiOCH ₃ , (C ₂ H ₅ ) ₃ SiOCH ₃ , _{C 3 H 7 (C 2 H} 5) 2 SiOCH 3, C 4 H 9 (C 2 H 5) 2 SiOCH 3, C 5 H 11 (C 2 H 5) 2 SiOCH 3, C 6 H 13 (C 2 H ₅ ) ₂ SiOCH ₃ , C ₇ H ₁₅ (C ₂ H ₅ ) ₂ SiOCH ₃ , C ₈ H ₁₇ (C ₂ H ₅ ) ₂ SiOCH ₃ , C ₉ H ₁₉ (C ₂ H ₅ ) ₂ SiOCH ₃ , C ₁₀ H ₂₁ (C ₂ H ₅ ) ₂ SiOCH ₃ , C ₁₁ H ₂₃ (C ₂ H ₅ ) ₂ SiOCH ₃ , C ₁₂ H ₂₅ (C ₂ H ₅ ) ₂ SiOCH ₃ , C ₁₃ H ₂₇ (C ₂ H ₅ ) ₂ SiOCH ₃ , C ₁₄ H ₂₉ (C ₂ H ₅ ) ₂ SiOCH ₃ , C ₁₅ H ₃₁ (C ₂ H ₅ ) ₂ SiOCH ₃ , C ₁₆ H ₃₃ (C ₂ H ₅ ) ₂ SiOCH ₃ , C ₁₇ H ₃₅ (C _{2 H 5) 2 SiOCH 3,} C 18 H 37 (C 2 H 5) 2 SiOCH 3, (C 4 H 9) 3 SiOCH 3, C 5 H 11 (C 4 H 9) 2 SiOCH 3, C 6 H 13 _{(C 4 H 9) 2 SiOCH} 3, C 7 H 15 (C 4 H 9) 2 SiOCH 3, C 8 H 17 (C 4 H 9) 2 SiOCH 3, C 9 H 19 (C 4 H 9) 2 _{iOCH 3, C 10 H 21 (} C 4 H 9) 2 SiOCH 3, C 11 H 23 (C 4 H 9) 2 SiOCH 3, C 12 H 25 (C 4 H 9) 2 SiOCH 3, C 13 H 27 ( _{C 4 H 9) 2 SiOCH 3} , C 14 H 29 (C 4 H 9) 2 SiOCH 3, C 15 H 31 (C 4 H 9) 2 SiOCH 3, C 16 H 33 (C 4 H 9) 2 SiOCH 3 , C ₁₇ H ₃₅ (C ₄ H ₉ ) ₂ SiOCH ₃ , C ₁₈ H ₃₇ (C ₄ H ₉ ) ₂ SiOCH ₃ , C ₅ H ₁₁ (CH ₃ ) Si (OCH ₃ ) ₂ , C ₆ H ₁₃ (CH _{3) Si (OCH 3) 2} , C 7 H 15 (CH 3) Si (OCH 3) 2, C 8 H 17 (CH 3) Si (OCH 3) 2, C 9 H 19 (CH 3) Si (OC _{H 3) 2, C 10 H} 21 (CH 3) Si (OCH 3) 2, C 11 H 23 (CH 3) Si (OCH 3) 2, C 12 H 25 (CH 3) Si (OCH 3) 2, _{C 13 H 27 (CH 3)} Si (OCH 3) 2, C 14 H 29 (CH 3) Si (OCH 3) 2, C 15 H 31 (CH 3) Si (OCH 3) 2, C 16 H 33 ( CH ₃ ) Si (OCH ₃ ) ₂ , C ₁₇ H ₃₅ (CH ₃ ) Si (OCH ₃ ) ₂ , C ₁₈ H ₃₇ (CH ₃ ) Si (OCH ₃ ) ₂ , C ₃ F ₇ C ₂ H ₄ (CH _{3) Si (OCH 3) 2} , C 4 F 9 C 2 H 4 (CH 3) Si (OCH 3) 2, C 5 F 11 C 2 H 4 (CH 3) Si (OCH 3) 2, C 6 F _{13 C 2 H 4 (CH 3} ) Si (OCH _{) 2, C 7 F 15 C} 2 H 4 (CH 3) Si (OCH 3) 2, C 8 F 17 C 2 H 4 (CH 3) Si (OCH 3) 2, C 6 H 13 Si (OCH 3) ₃ , C ₇ H ₁₅ Si (OCH ₃ ) ₃ , C ₈ H ₁₇ Si (OCH ₃ ) ₃ , C ₉ H ₁₉ Si (OCH ₃ ) ₃ , C ₁₀ H ₂₁ Si (OCH ₃ ) ₃ , C ₁₁ H ₂₃ Si (OCH ₃ ) ₃ , C ₁₂ H ₂₅ Si (OCH ₃ ) ₃ , C ₁₃ H ₂₇ Si (OCH ₃ ) ₃ , C ₁₄ H ₂₉ Si (OCH ₃ ) ₃ , C ₁₅ H ₃₁ Si (OCH ₃ ) ₃ C ₁₆ H ₃₃ Si (OCH ₃ ) ₃ , C ₁₇ H ₃₅ Si (OCH ₃ ) ₃ , C ₁₈ H ₃₇ Si (OCH ₃ ) ₃ , C ₄ F ₉ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₅ F ₁₁ C ₂ H _{Si (OCH 3) 3, C} 6 F 13 C 2 H 4 Si (OCH 3) 3, C 7 F 15 C 2 H 4 Si (OCH 3) 3, C 8 F 17 C 2 H 4 Si (OCH 3
) ₃ , C ₄ H ₉ (CH ₃ ) ₂ SiOC ₂ H ₅ , C ₅ H ₁₁ (CH ₃ ) ₂ SiOC ₂ H ₅ , C ₆ H ₁₃ (CH ₃ ) ₂ SiOC ₂ H ₅ , C ₇ H ₁₅ ( _{CH 3) 2 SiOC 2 H 5} , C 8 H 17 (CH 3) 2 SiOC 2 H 5, C 9 H 19 (CH 3) 2 SiOC 2 H 5, C 10 H 21 (CH 3) 2 SiOC 2 H 5 C ₁₁ H ₂₃ (CH ₃ ) ₂ SiOC ₂ H ₅ , C ₁₂ H ₂₅ (CH ₃ ) ₂ SiOC ₂ H ₅ , C ₁₃ H ₂₇ (CH ₃ ) ₂ SiOC ₂ H ₅ , C ₁₄ H ₂₉ (CH _{3 ) 2 SiOC 2 H 5, C} 15 H 31 (CH 3) 2 SiOC 2 H 5, C 16 H 33 (CH 3) 2 SiOC 2 H 5, C 17 H 35 (CH 3) 2 SiOC 2 H 5, _{18 H 37 (CH 3) 2} SiOC 2 H 5, C 2 F 5 C 2 H 4 (CH 3) 2 SiOC 2 H 5, C 3 F 7 C 2 H 4 (CH 3) 2 SiOC 2 H 5, C _{4 F 9 C 2 H 4 (} CH 3) 2 SiOC 2 H 5, C 5 F 11 C 2 H 4 (CH 3) 2 SiOC 2 H 5, C 6 F 13 C 2 H 4 (CH 3) 2 SiOC 2 _{H 5, C 7 F 15 C} 2 H 4 (CH 3) 2 SiOC 2 H 5, C 8 F 17 C 2 H 4 (CH 3) 2 SiOC 2 H 5, (C 2 H 5) 3 SiOC 2 H 5 _{, C 3 H 7 (C 2} H 5) 2 SiOC 2 H 5, C 4 H 9 (C 2 H 5) 2 SiOC 2 H 5, C 5 H 11 (C 2 H 5) 2 SiOC 2 H 5, C _{6 H 13 (C 2 H 5} ) 2 SiOC 2 H 5 _{C 7 H 15 (C 2 H} 5) 2 SiOC 2 H 5, C 8 H 17 (C 2 H 5) 2 SiOC 2 H 5, C 9 H 19 (C 2 H 5) 2 SiOC 2 H 5, C 10 _{H 21 (C 2 H 5)} 2 SiOC 2 H 5, C 11 H 23 (C 2 H 5) 2 SiOC 2 H 5, C 12 H 25 (C 2 H 5) 2 SiOC 2 H 5, C 13 H 27 _{(C 2 H 5) 2 SiOC} 2 H 5, C 14 H 29 (C 2 H 5) 2 SiOC 2 H 5, C 15 H 31 (C 2 H 5) 2 SiOC 2 H 5, C 16 H 33 (C _{2 H 5) 2 SiOC 2 H} 5, C 17 H 35 (C 2 H 5) 2 SiOC 2 H 5, C 18 H 37 (C 2 H 5) 2 SiOC 2 H 5, (C 4 H 9) 3 SiOC ₂ H ₅ , C ₅ H ₁₁ (C ₄ H ₉ ) ₂ SiOC ₂ H ₅ , C ₆ H ₁₃ (C ₄ H ₉ ) ₂ SiOC ₂ H ₅ , C ₇ H ₁₅ (C ₄ H ₉ ) ₂ SiOC ₂ H ₅ , C ₈ H ₁₇ (C ₄ H ₉ ) ₂ SiOC ₂ H ₅ , C ₉ H ₁₉ (C ₄ H ₉ ) ₂ SiOC ₂ H ₅ , C ₁₀ H ₂₁ (C ₄ H ₉ ) ₂ SiOC ₂ H ₅ , C ₁₁ H ₂₃ (C ₄ H ₉ ) _{2 SiOC 2 H 5, C 12 H} 25 (C 4 H 9) 2 SiOC 2 H 5, C 13 H 27 (C 4 H 9) 2 SiOC 2 H 5, C 14 H 29 (C 4 H 9) 2 SiOC 2 _{H 5, C 15 H 31 (} C 4 H 9) 2 SiOC 2 H 5, C 16 H 33 (C 4 H 9) 2 SiOC 2 H 5, C 17 H 35 (C 4 H 9) 2 SiOC 2 H 5 _{, C 18 H 37 (C 4} H 9 _{2 SiOC 2 H 5, C 5} H 11 (CH 3) Si (OC 2 H 5) 2, C 6 H 13 (CH 3) Si (OC 2 H 5) 2, C 7 H 15 (CH 3) Si ( _{OC 2 H 5) 2, C} 8 H 17 (CH 3) Si (OC 2 H 5) 2, C 9 H 19 (CH 3) Si (OC 2 H 5) 2, C 10 H 21 (CH 3) Si (OC ₂ H ₅ ) ₂ , C ₁₁ H ₂₃ (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , C ₁₂ H ₂₅ (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , C ₁₃ H ₂₇ (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , C ₁₄ H ₂₉ (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , C ₁₅ H ₃₁ (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , C ₁₆ H ₃₃ (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , C ₁₇ H ₃₅ (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , C ₁₈ H ₃₇ (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , C ₃ F ₇ C ₂ H ₄ (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , C ₄ F _{9 C 2 H 4 (CH 3)} Si (OC 2 H 5) 2, C 5 F 11 C 2 H 4 (CH 3) Si (OC 2 H 5) 2, C 6 F 13 C 2 H 4 (CH 3) Si (OC ₂ H ₅ ) ₂ , C ₇ F ₁₅ C ₂ H ₄ (CH ₃ ) Si (OC ₂ H ₅ ) ₂ , C ₈ F ₁₇ C ₂ H ₄ (CH ₃ ) Si (OC ₂ H ₅ ) _{2 , C 6 H 13 Si (OC} 2 H 5) 3, C 7 H 15 Si (OC 2 H 5) 3, C 8 H 17 Si (OC 2 H 5) 3, C 9 H 19 Si (OC 2 H 5 _{) 3, C 10 H 21 Si} (OC 2 H 5) 3, C 11 H 23 Si (OC 2 H 5) _{, C 12 H 25 Si (OC} 2 H 5) 3, C 13 H 27 Si (OC 2 H 5) 3, C 14 H 29 Si (OC 2 H 5) 3, C 15 H 31 Si (OC 2 H 5 ) ₃ , C ₁₆ H ₃₃ Si (OC ₂ H ₅ ) ₃ , C ₁₇ H ₃₅ Si (OC ₂ H ₅ ) ₃ , C ₁₈ H ₃₇ Si (OC ₂ H ₅ ) ₃ , C ₄ F ₉ C ₂ H _{4 Si (OC 2 H 5) 3} , C 5 F 11 C 2 H 4 Si (OC 2 H 5) 3, C 6 F 13 C 2 H 4 Si (OC 2 H 5) 3, C 7 F 15 C 2 H ₄ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇
Examples thereof include alkoxysilane compounds such as C ₂ H ₄ Si (OC ₂ H ₅ ) ₃ .

Also, for example, 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, 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 ( _{C 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, 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 (NCO) 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 , 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, C ₆ H ₁₃ Si (NCO) ₃ , C ₇ H ₁₅ Si (N CO) 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, 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 Examples include isocyanate silane compounds such as 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 .

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 2 F 5 C 2 H 4 (C _{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 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 _{H, [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, [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 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 _{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 Si N (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) _{i [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 _{) 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 Si _{(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 ₄ F ₉ 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 S _{N (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 Examples thereof include aminosilane compounds such as ₁₇ H ₃₅ (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 .

  Among these silicon compounds, when a hydrogen atom of a hydrocarbon group is substituted with a halogen atom, the halogen atom to be substituted is preferably a fluorine atom in consideration of water repellency.

In addition, the monovalent functional group represented by X in the general formula [1] whose element bonded to the silicon element is nitrogen is carbon, hydrogen, boron, nitrogen, phosphorus, oxygen, sulfur, silicon, germanium, fluorine , chlorine, bromine, from the elements such as iodine, may be a configured functional groups, 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 group, —N (C ₂ H ₅ ) ₂ group, —N (C ₃ H ₇ ) ₂ group, —N (CH ₃ ) (C ₂ H ₅ ) Group, —NH (C ₂ H ₅ ) group, —NCO group, imidazole group, acetamide group and the like.

Furthermore, the monovalent functional group represented by X in the general formula [1] whose element bonded to the silicon element is oxygen is carbon, hydrogen, boron, nitrogen, phosphorus, oxygen, sulfur, silicon, germanium, fluorine , Chlorine, bromine and iodine functional groups, for example, —OCH ₃ group, —OC ₂ H ₅ group, —OC ₃ H ₇ group, —OCOCH ₃ group, —OCOCF ₃ group, etc. Is mentioned.

  Examples of the halogen group represented by X in the general formula [1] include -F group, -Cl group, -Br group, and -I group. Of these, a -Cl group is more preferred.

  Further, a in the general formula [1] may be an integer of 1 to 3, but when a is 1 or 2, if the water-repellent protective film forming agent or the chemical solution is stored for a long period of time, mixing of moisture, etc. As a result, polymerization of the silicon compound occurs, and the storage period may be shortened. Considering this, it is preferable that a in the general formula [1] is 3.

Among the silicon compounds represented by the general formula [1], R ¹ is composed of one hydrocarbon group having 4 to 18 carbon atoms which is unsubstituted or substituted with a halogen atom and two methyl groups (that is, The compound represented by the general formula [3] is preferable because the reaction rate with the hydroxyl group on the uneven pattern surface or wafer surface is increased. This is because the steric hindrance by the hydrophobic group has a great influence on the reaction rate in the reaction of the hydroxyl group on the uneven pattern surface or the wafer surface with the silicon compound, and the longest alkyl chain bonded to the silicon element is This is because the remaining two except for are preferably shorter.

Therefore, among the silicon compounds represented by the general formula [1] described above, particularly preferable compounds include C ₄ H ₉ (CH ₃ ) ₂ SiCl, C ₅ H ₁₁ (CH ₃ ) ₂ SiCl, and 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 Si _{l, 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 Si N (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, the water repellent protective film forming agent may contain two or more types of silicon compounds represented by the general formula [1], or the silicon compound represented by the general formula [1]. And a silicon compound other than the silicon compound represented by the general formula [1].

  Next, the water repellent protective film forming chemical solution of the present invention will be described. The chemical solution only needs to contain at least the water-repellent protective film forming agent, and an organic solvent can be used as the solvent for the chemical solution. The organic solvent only needs to dissolve the protective film forming agent. For example, hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, alcohols, polyhydric alcohol derivatives. Nitrogen-containing compound solvents are preferably used. When water is used as a solvent, the reactive site of the silicon compound in the chemical solution (X in the general formula [1]) is hydrolyzed with water to form a silanol group (Si—OH). In order to react with this silanol group, silicon compounds are bonded to each other to form a dimer. Since this dimer has low reactivity with the concavo-convex pattern surface and the hydroxyl group on the wafer surface, it takes a long time to make the concavo-convex pattern surface and the wafer surface water-repellent, so use water as a solvent. Is not preferred.

  Furthermore, since the silicon compound easily reacts with a protic solvent, it is particularly preferable to use an aprotic solvent as the organic solvent because water repellency is easily developed in a short time. The aprotic solvent is both an aprotic polar solvent and an aprotic apolar solvent. Examples of such aprotic solvents include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, polyhydric alcohol derivatives having no hydroxyl group, and nitrogen-containing compounds having no N—H bond. Compound solvents are mentioned. 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 acetoacetate, and the ether. Examples of such classes include diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, and dioxane.Examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, and methyl butyl ketone. Examples of halogen solvents include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, 1, 1, 1, 3, 3-pentafluorobutane, Hydrofluorocarbons such as Kutafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeolora H (manufactured by Nippon Zeon Co., Ltd.), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether Asahi Clin AE-3000 (manufactured by Asahi Glass Co., Ltd.), Novec HFE-7100, Novec HFE-7200, Novec 7300, and Novec 7600 (all manufactured by 3M Corporation), hydrofluoroethers such as tetrachloromethane, chlorocarbons such as tetrachloromethane, and chloroform Hydrochlorocarbons, chlorofluorocarbons such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3,3-pentaph Oropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoro There are hydrochlorofluorocarbons such as propene, perfluoroethers, perfluoropolyethers, etc. Examples of the sulfoxide solvents include dimethyl sulfoxide, and examples of the polyhydric alcohol derivatives having no hydroxyl group include diethylene glycol mono Ethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl Ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, dipropylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, etc. Examples of the nitrogen-containing compound solvent having no N—H bond include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, triethylamine, and pyridine.

  The organic solvent may be present as long as it is a trace amount of water. However, when this moisture is contained in a large amount in the solvent, the silicon compound may be hydrolyzed by the moisture to reduce the reactivity. For this reason, it is preferable to reduce the amount of water in the solvent, and the amount of water is preferably less than 1 mole in terms of molar ratio to the silicon compound when mixed with the silicon compound. It is particularly preferable to make it less than 5 mole times.

  In addition, a catalyst may be added to the chemical solution in order to promote the reaction between the silicon compound, which is a protective film forming agent, and the hydroxyl group on the uneven pattern surface or the wafer surface. Such catalysts include trifluoroacetic acid, trifluoroacetic anhydride, pentafluoropropionic acid, pentafluoropropionic anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, sulfuric acid, hydrogen chloride-free acid, ammonia, etc. Bases such as alkylamine, N, N, N ′, N′-tetramethylethylenediamine, triethylenediamine, dimethylaniline, pyridine, piperazine, N-alkylmorpholine, potassium acetate, potassium salt, methylhydroxyamine hydrochloride, And metal complexes and metal salts, such as tin, aluminum, and titanium, are used suitably. In particular, considering the catalytic effect, acids such as trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, sulfuric acid, and hydrogen chloride are preferable, and the acid does not contain moisture. Is preferred.

In particular, when the number of carbon atoms of the hydrophobic group R ¹ in the general formula [1] increases, the reaction rate with the concavo-convex pattern surface or the hydroxyl group on the wafer surface may decrease due to steric hindrance. In this case, by adding an acid that does not contain water as a catalyst, the reaction between the surface of the concave / convex pattern and the surface of the wafer and the silicon compound is promoted, which compensates for a decrease in reaction rate due to steric hindrance due to hydrophobic groups. There is a case.

  The addition amount of the catalyst is preferably 0.01 to 100% by mass with respect to 100% by mass of the total amount of the silicon compound. If the amount added is small, the catalytic effect is lowered, which is not preferable. Moreover, even if it adds excessively, a catalyst effect will not improve, but when it increases more than a silicon compound, a catalyst effect may fall conversely. Further, there is a concern that the impurities remain on the surface of the concave / convex pattern or the wafer surface as impurities. For this reason, 0.01-100 mass% is preferable, and, as for the said catalyst addition amount, More preferably, it is 0.1-50 mass%.

  Further, the silicon compound is preferably mixed so as to be 0.1 to 50% by mass with respect to 100% by mass of the total amount of the chemical solution, and more preferably 0% with respect to 100% by mass of the total amount of the chemical solution. 3 to 20% by mass. When the silicon compound is less than 0.1% by mass, it reacts with moisture contained in a trace amount in the organic solvent and deactivates. Therefore, the ability to form a water-repellent protective film is poor, and the uneven pattern surface or wafer surface is It cannot be sufficiently water-repellent. On the other hand, when it is more than 50% by mass, there is a concern that it may remain as an impurity on the surface of the concavo-convex pattern or the wafer, and it is not preferable from the viewpoint of cost.

  The chemical solution of the present invention may be a one-component type in which the silicon compound and the catalyst are mixed from the beginning, or a two-component type in which the silicon compound and the catalyst are mixed. You may do.

  Next, the wafer cleaning method of the present invention will be described.

  In general, a wafer containing silicon to be cleaned using the chemical solution of the present invention is often one that has undergone a pretreatment step in which the wafer surface is a surface having an uneven pattern.

The method is not limited as long as a pattern can be formed on the wafer surface by the pretreatment step. As a general method, after applying a resist on the wafer surface, the resist is exposed through a resist mask, and the exposed resist or the resist having a desired uneven pattern is removed by etching away the unexposed resist. Is made. Moreover, the resist which has an uneven | corrugated pattern can be obtained also by pressing the mold which has a pattern to a resist. Next, the wafer is etched. At this time, the wafer surface corresponding to the concave portion of the resist pattern is selectively etched. Finally, when the resist is removed, a silicon wafer having a concavo-convex pattern is obtained.

  The wafer may be a silicon wafer, a silicon oxide film formed on a silicon wafer by a thermal oxidation method, a CVD method, a sputtering method, or the like, or a silicon nitride film or polysilicon by a CVD method, a sputtering method, or the like. Those having a film formed thereon, and those silicon nitride films and polysilicon films, or those in which the silicon wafer surface is naturally oxidized are also included. Further, a wafer composed of a plurality of components containing silicon and / or silicon oxide, a silicon carbide wafer, and a wafer in which various films containing a silicon element are formed on the wafer can be used as the wafer. Further, various films containing silicon elements may be formed on a wafer not containing silicon elements, such as sapphire wafers, various compound semiconductor wafers, and plastic wafers. The chemical solution contains silicon atoms in a wafer surface containing silicon element, a film surface containing silicon element formed on the wafer, and a concavo-convex pattern containing silicon element formed from the wafer or the film. A protective film can be formed on the surface of the part to make it water repellent.

  In general, a wafer having a silicon oxide film or a silicon oxide portion on its surface has many hydroxyl groups that are reactive sites on the surface, so that water repellency is easily imparted. On the other hand, a wafer having a silicon nitride film or a silicon nitride portion on the surface, a wafer having a polysilicon film or a polysilicon portion, or a silicon wafer has few hydroxyl groups on the surface, and the conventional technology provides water repellency. It was difficult to do. However, even with such a wafer, when the chemical solution of the present invention is used, sufficient water repellency can be imparted to the wafer surface, and as a result, the effect of preventing pattern collapse during cleaning can be achieved. Therefore, not only a wafer having a silicon oxide film or a silicon oxide portion on the surface, but also a wafer having a silicon nitride film or a silicon nitride portion, a wafer having a polysilicon film or a polysilicon portion, or a silicon wafer is used for the chemical solution of the present invention. It is suitable for application and is a preferable base material, and a wafer having many silicon nitride films and silicon nitride portions is particularly preferable.

The present invention is a method for cleaning a wafer containing a silicon element on at least a concave surface of the concavo-convex pattern in a wafer having a concavo-convex pattern formed on the surface,
A water-based cleaning liquid cleaning step for cleaning the wafer surface with a water-based cleaning liquid. A liquid removing step of removing the liquid on the wafer surface; a water repellent protective film removing step of removing the water repellent protective film from the surface of the recess.

  Examples of the aqueous cleaning liquid include water or water in which at least one of organic solvents, acids, alkalis, surfactants, hydrogen peroxide, and ozone is mixed in water as a main component (for example, containing water). And a ratio of 50% by mass or more).

  In the cleaning with the aqueous cleaning liquid, after removing the resist and removing particles on the wafer surface, when removing the aqueous cleaning liquid by drying or the like, the pattern collapses if the width of the concave portion is small and the aspect ratio of the convex portion is large. Is likely to occur. The concavo-convex pattern is defined as shown in FIGS. FIG. 1 is a schematic view of a wafer 1 whose surface has a concavo-convex pattern 2 as viewed from the perspective, and FIG. 2 shows a part of the a-a ′ cross section in FIG. 1. As shown in FIG. 2, the width 5 of the concave portion is indicated by the interval between the convex portion 3 and the convex portion 3, and the aspect ratio of the convex portion is expressed by dividing the height 6 of the convex portion by the width 7 of the convex portion. Is done. Pattern collapse in the cleaning process tends to occur when the width of the recess is 70 nm or less, particularly 45 nm or less, and the aspect ratio is 4 or more, particularly 6 or more.

  Furthermore, in the aqueous cleaning liquid cleaning step, in the portion containing silicon nitride or polysilicon where the aqueous cleaning liquid is held and contacted, a part of the surface is oxidized and a hydroxyl group is formed by contact with the aqueous cleaning liquid. Since the water-repellent protective film forming agent provided in the present invention has a strong hydrophobic group, an excellent water-repellent protective film is formed even if a small amount of the water-repellent protective film-forming agent reacts with some of the hydroxyl groups formed by oxidation. Can be formed.

  This oxidation of the wafer surface proceeds even if the aqueous cleaning solution is pure water at room temperature, but it tends to proceed more easily if the aqueous cleaning solution is strongly acidic or the temperature of the aqueous cleaning solution is high. The acid may be added to the aqueous cleaning solution, or the temperature of the aqueous cleaning solution may be increased. Furthermore, hydrogen peroxide or ozone may be added for the purpose of promoting oxidation.

In the wafer cleaning method of the present invention, in order to perform efficient cleaning without causing pattern collapse, the water-repellent protective film forming step from the water-based cleaning solution cleaning step is always held in at least the concave portion of the wafer. It is preferable to carry out in the state. In addition, when the water-repellent protective film-forming chemical solution held in the concave portion of the wafer is replaced with another liquid after the water-repellent protective film forming step, the liquid is always held in at least the concave portion of the wafer as described above. It is preferable to carry out in the state. In the present invention, the cleaning method of the wafer is not particularly limited as long as the aqueous cleaning liquid, the chemical liquid, and other liquids can be held in at least the concave portions of the concave / convex pattern of the wafer. As a wafer cleaning method, a wafer cleaning method represented by spin cleaning in which a wafer is cleaned one by one by supplying liquid to the vicinity of the rotation center while rotating the wafer while holding the wafer substantially horizontal, or a plurality of cleaning methods in the cleaning tank. One example is a batch system in which a single wafer is immersed and washed. Incidentally, the aqueous cleaning solution at least concave portions of the concavo-convex pattern of the wafer, the aqueous cleaning solution at the time of supplying the drug solution or other liquid, the form of the drug solution or other liquid becomes liquid when it is held in the recess There is no particular limitation as long as it is, and examples thereof include liquid and vapor.

  Next, the water repellent protective film forming step will be described. The transition from the water-based cleaning liquid cleaning step to the water-repellent protective film forming step is to replace the water-based cleaning liquid held in at least the concave portion of the concave / convex pattern of the wafer in the water-based cleaning liquid cleaning step with the chemical solution for forming the water-repellent protective film. Done in In the replacement of the water-based cleaning liquid with the water-repellent protective film-forming chemical liquid, it may be replaced directly or after being replaced once or more by a different cleaning liquid A (hereinafter sometimes simply referred to as “cleaning liquid A”). Alternatively, a chemical solution for forming a water repellent protective film may be substituted. Preferable examples of the cleaning liquid A include water, an organic solvent, a mixture of water and an organic solvent, or a mixture of at least one of acid, alkali, and surfactant. Examples of the organic solvent that is one of the preferred examples of the cleaning liquid A include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, alcohols, polyhydric alcohol derivatives, And nitrogen-containing compound solvents.

  The formation of the water-repellent protective film in the water-repellent protective film forming step is performed by holding a water-repellent protective film-forming chemical solution in at least the concave portion of the concave-convex pattern of the wafer. FIG. 3 is a schematic view showing a state in which the concave portion 4 holds the chemical solution 8 for forming the water repellent protective film. The wafer in the schematic diagram of FIG. 3 shows a part of the a-a ′ cross section of FIG. 1. In the water repellent protective film forming step, a chemical solution for forming the water repellent protective film is supplied to the wafer 1 on which the concave / convex pattern 2 is formed. At this time, the water-repellent protective film-forming chemical solution is held in at least the concave portion 4 as shown in FIG. 3, and the surface of the concave portion 4 is water-repellent. Note that the protective film of the present invention does not necessarily have to be formed continuously, and does not necessarily have to be formed uniformly, but because it can impart better water repellency, More preferably, it is uniformly formed.

  Further, in the protective film forming step, if the temperature of the chemical solution is increased, the protective film can be easily formed in a shorter time, but the stability of the chemical solution may be impaired due to boiling or evaporation of the chemical solution for forming the water repellent protective film. Therefore, the chemical solution is preferably held at 10 to 160 ° C., particularly preferably 15 to 120 ° C.

FIG. 4 shows a schematic diagram in the case where the liquid 9 is held in the recess 4 that has been made water-repellent by the water-repellent protective film forming chemical. The wafer in the schematic diagram of FIG. 4 shows a part of the aa ′ cross section of FIG. A water repellent protective film 10 is formed on the surface of the recess 4. At this time, the liquid 9 held in the recess 4 may be the above-described chemical liquid or a liquid (cleaning liquid B) after the chemical liquid is replaced with a different cleaning liquid B (hereinafter sometimes simply referred to as “cleaning liquid B”). , A liquid in the middle of substitution (mixed liquid of the chemical solution and the cleaning solution B ) may be used. The water repellent protective film 10 is held on the wafer surface even when the liquid 9 is removed from the recess 4.

  Preferable examples of the cleaning liquid B include water, an organic solvent, a mixture of water and an organic solvent, or a mixture of at least one of acid, alkali, and surfactant. Examples of the organic solvent that is one of the preferred examples of the cleaning liquid B include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, alcohols, polyhydric alcohols, many And derivatives of polyhydric alcohols, nitrogen-containing compound solvents, and the like.

  When the liquid is held in the concave portion of the wafer having the concave / convex pattern, a capillary force acts on the concave portion. The magnitude of this capillary force is the absolute value of P obtained by the following formula.

P = 2 × γ × cos θ / S
(Wherein γ is the surface tension of the liquid held in the recess, θ is the contact angle between the recess surface and the liquid held in the recess, and S is the width of the recess.)
When a water-repellent protective film exists on the surface of the recess as in the recess 4 of FIG. 4, θ is increased and the absolute value of P is decreased. From the viewpoint of suppressing pattern collapse, the smaller the absolute value of P, the better. It is ideal to adjust the contact angle with the liquid to be removed to around 90 ° to bring the capillary force as close as possible to 0.0 MN / m ^2. It is.

  As shown in FIG. 4, when the protective film 10 is formed on the surface of the recess, the contact angle on the assumption that water is held on the surface is preferably 65 to 115 ° because pattern collapse hardly occurs. The closer the contact angle is to 90 °, the smaller the capillary force acting on the recess and the more difficult the pattern collapse occurs, so 70 to 110 ° is particularly preferable.

Next, the liquid removal process will be described. The liquid held in the recess is the chemical liquid, the cleaning liquid B, or a mixed liquid of the chemical liquid and the cleaning liquid B. As a method for removing the liquid, known drying methods such as natural drying, air drying, N ₂ gas drying, spin drying method, IPA (2-propanol) vapor drying, Marangoni drying, heat drying, hot air drying, vacuum drying, etc. It is preferable to carry out by. In order to efficiently remove the liquid, the retained liquid may be drained and removed, and then the remaining liquid may be dried.

  Finally, the water repellent protective film removing step will be described. When removing the water-repellent protective film, it is effective to cut the C—C bond and C—F bond in the protective film. The method is not particularly limited as long as it can cut the bond, for example, irradiating the wafer surface with light, heating the wafer, exposing the wafer to ozone, irradiating the wafer surface with plasma, For example, corona discharge on the wafer surface may be mentioned.

  When the protective film is removed by light irradiation, wavelengths shorter than 340 nm and 240 nm, which are energy equivalent to 83 kcal / mol and 116 kcal / mol, which are binding energies of C—C bonds and C—F bonds in the protective film. It is preferable to irradiate ultraviolet rays containing. As this light source, a metal halide lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an excimer lamp, a carbon arc, or the like is used.

  Further, when the protective film is removed by light irradiation, if the constituent components of the protective film are decomposed by ultraviolet rays and ozone is generated at the same time, and the constituent components of the protective film are oxidized and volatilized by the ozone, the processing time is shortened. Therefore, it is particularly preferable. As this light source, a low-pressure mercury lamp, an excimer lamp, or the like may be used. Further, the wafer may be heated while irradiating light.

  When the wafer is heated, it is preferable to heat the wafer at 400 to 700 ° C, preferably 500 to 700 ° C. The heating time is preferably 1 to 60 minutes, preferably 10 to 30 minutes. In this process, ozone exposure, plasma irradiation, corona discharge, etc. may be used in combination. Further, light irradiation may be performed while heating the wafer.

  Methods for removing the protective film by heating include a method of bringing a wafer into contact with a heat source and a method of placing the wafer in a heated atmosphere such as a heat treatment furnace. The method of placing the wafer in a heated atmosphere is easy to operate because it is easy to uniformly apply energy for removing the protective film to the wafer surface even when processing a plurality of wafers. This is an industrially advantageous method that requires a short processing time and a high processing capacity.

  When the wafer is exposed to ozone, ozone generated by ultraviolet irradiation with a low-pressure mercury lamp or the like or low-temperature discharge with a high voltage may be provided to the wafer surface. The wafer may be irradiated with light while being exposed to ozone, or may be heated.

  By combining the light irradiation, heating, ozone exposure, plasma irradiation, and corona discharge, the protective film on the wafer surface can be efficiently removed.

  Making the surface of the wafer a surface having a concavo-convex pattern, replacing the cleaning liquid held at least in the concave portion of the concavo-convex pattern with another cleaning liquid, various studies have been made in other literatures, etc. and already established techniques Thus, in this example, the evaluation was mainly performed on the protective film forming chemical solution.

  The capillary force acting on the concave portion of the concave / convex pattern is represented by the following formula.

P = 2 × γ × cos θ / S
(Wherein γ is the surface tension of the liquid held in the recess, θ is the contact angle between the recess surface and the liquid held in the recess, and S is the width of the recess.)
As is apparent from this equation, the capillary force P that causes pattern collapse greatly depends on the contact angle of the cleaning liquid to the wafer surface, that is, the contact angle of the droplets and the surface tension of the cleaning liquid. For cleaning liquid retained in the recess 4 of the uneven pattern 2, and the contact angle of the droplet, since the capillary force exerted on it recess which considered as equivalent to a pattern collapse are correlated, the formula and water-repellent The capillary force can be derived from the evaluation of the contact angle of the droplet of the protective film 10. In the examples, water, which is a typical aqueous cleaning solution, was used as the cleaning solution. From the above formula, as the contact angle is closer to 90 °, the capillary force acting on the concave portion becomes smaller and the pattern collapse hardly occurs. Therefore, the contact angle when assuming that water is held on the surface of the protective film is 65 ˜115 ° is preferable, and 70 to 110 ° is particularly preferable.

  As described in JIS R 3257 “Test method for wettability of substrate glass surface”, the contact angle of water droplets was evaluated by dropping several μl of water droplets on the surface of the sample substrate, and measuring the angle between the water droplet and the substrate surface. Made by measurement. However, in the case of a wafer having a pattern, the contact angle becomes very large. This is because a Wenzel effect and a Cassie effect occur, and the contact angle is affected by the surface shape (roughness) of the substrate, and the apparent contact angle of water droplets increases. Therefore, in the case of a wafer having a concavo-convex pattern on the surface, the contact angle of the protective film 10 itself formed on the concavo-convex pattern surface cannot be accurately evaluated.

Therefore, in this embodiment, the chemical solution is applied to a wafer having a smooth surface, a protective film is formed on the wafer surface, and the protective film is formed on the surface of the wafer 1 on which the uneven pattern 2 is formed. The film 10 was considered and various evaluations were performed. In this example, the wafer having a smooth surface is a “silicon wafer with a SiO ₂ film” (expressed as SiO _{2 in the} table) having a silicon oxide layer on a silicon wafer having a smooth surface, and the surface is smooth. A “SiN film-attached silicon wafer” (expressed as SiN in the table) having a silicon nitride layer on a silicon wafer was used.

  Details are described below. In the following, a method for evaluating a wafer provided with a chemical solution for forming a protective film, preparation of the chemical solution for forming the protective film, and an evaluation result after providing the chemical solution for forming a protective film on the wafer are described.

[Evaluation method of wafer provided with chemical solution for forming protective film]
The following evaluations (1) to (3) were performed as methods for evaluating a wafer provided with a chemical solution for forming a protective film.

(1) Contact angle evaluation of the protective film formed on the wafer surface About 2 μl of pure water is placed on the wafer surface on which the protective film is formed, and the angle between the water droplet and the wafer surface is measured by a contact angle meter (manufactured by Kyowa Interface Science: CA-X type) was used as the contact angle. Here, the protective film having a contact angle in the range of 65 to 115 ° was regarded as acceptable.

(2) Removability of protective film The sample was irradiated with UV light from a low-pressure mercury lamp for 1 minute under the following conditions to evaluate the removability of the protective film in the water-repellent protective film removal step. A sample having a water droplet contact angle of 10 ° or less after irradiation was regarded as acceptable (denoted as “◯” in the table).

・ Lamp: Sen Special Light Source PL2003N-10
Illuminance: 15 mW / cm ² (distance from light source to sample is 10 mm)
(3) Evaluation of surface smoothness of wafer after removal of protective film Surface observation was performed with an atomic force electron microscope (Seiko-Electronics: SPI3700, 2.5 μm square scan), and centerline average surface roughness: Ra (nm) was determined. Asked. Ra is a three-dimensional extension of the centerline average roughness defined in JIS B 0601 applied to the measurement surface. “The absolute value of the difference from the reference surface to the specified surface is averaged. The value was calculated by the following formula. If the Ra value of the wafer surface after removing the protective film is 1 nm or less, the wafer surface is not eroded by cleaning, and the residue of the protective film is not present on the wafer surface. Notation) .

formula

ここで、Ｘ_Ｌ、Ｘ_Ｒ、Ｙ_Ｂ、Ｙ_Ｔは、それぞれ、Ｘ座標、Ｙ座標の測定範囲を示す。Ｓ_０は、測定面が理想的にフラットであるとした時の面積であり、（Ｘ_Ｒ−Ｘ_Ｌ）×（Ｙ_Ｂ−Ｙ_Ｔ）の値とした。また、Ｆ（Ｘ，Ｙ）は、測定点（Ｘ，Ｙ）における高さ、Ｚ_０は、測定面内の平均高さを表す。

Here, X _L , X _R , Y _B , and Y _T indicate measurement ranges of the X coordinate and the Y coordinate, respectively. S ₀ is an area when the measurement surface is ideally flat, and is a value of (X _R −X _L ) × (Y _B −Y _T ). Moreover, F (X, Y) is, the measurement point (X, Y) in height, _{Z 0} represents the average height within the measurement surface.

[Example 1]
(1) Preparation of chemical solution for forming protective film Nonafluorohexyldimethylchlorosilane [C ₄ F ₉ (CH ₂ ) ₂ (CH ₃ ) ₂ SiCl] as protective film forming agent; 1 g, hydrofluoroether (manufactured by 3M) as organic solvent HFE-7100); 96 g, propylene glycol monomethyl ether acetate (PGMEA); 3 g are mixed (the organic solvent is expressed as HFE7100 / PGMEA in Table 1), and stirred for about 5 minutes. A protective film forming chemical solution having a concentration of the protective film forming agent with respect to the total amount (hereinafter referred to as “protective film forming agent concentration”) of 1% by mass was obtained.

(2) Cleaning of wafer A silicon wafer with a smooth silicon oxide film (a silicon wafer having a thermal oxide film layer having a thickness of 1 μm on the surface) is immersed in a 1% by mass hydrofluoric acid aqueous solution for 2 minutes and then in pure water for 1 minute. And immersed in 2-propanol for 1 minute. Further, a silicon wafer with a silicon nitride film (a silicon wafer having a silicon nitride layer with a thickness of 50 nm on the surface) produced by LP-CVD was immersed in a 1% by mass hydrofluoric acid aqueous solution for 2 minutes, and then immersed in pure water for 1 minute. 28% by mass ammonia water: 30% by mass hydrogen peroxide water: water was mixed at a volume ratio of 1: 1: 5, and the temperature was set to 70 ° C. with a hot plate for 1 minute, with pure water for 1 minute, 2 -Soaked in propanol for 1 minute.

(3) Surface treatment with a chemical film for forming a protective film on the wafer surface The silicon wafer with a silicon oxide film and the silicon wafer with a silicon nitride film were prepared in the above-mentioned "(1) Preparation of chemical liquid for forming a protective film". It was immersed for 1 minute at 20 degreeC in the chemical | medical solution for protective film formation. Thereafter, the wafer was immersed in 2-propanol for 1 minute, and then immersed in pure water for 1 minute. Finally, the wafer was taken out from the pure water and air was blown to remove the pure water on the surface.

  Each wafer obtained was evaluated in the manner described in “Method for evaluating wafer provided with chemical for forming protective film”. As shown in Table 1, in silicon wafer with silicon oxide film, initial contact before surface treatment was performed. Although the angle was less than 10 °, the contact angle after the surface treatment was 101 °, indicating an excellent water repellency imparting effect. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no residue of the water-repellent protective film remained after UV irradiation.

  On the other hand, in the silicon wafer with a silicon nitride film, the initial contact angle before the surface treatment was less than 10 °, but the contact angle after the surface treatment was 94 °, indicating an excellent water repellency imparting effect. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no residue of the water-repellent protective film remained after UV irradiation.

As described above, when nonafluorohexyldimethylchlorosilane [C ₄ F ₉ (CH ₂ ) ₂ (CH ₃ ) ₂ SiCl] is used as a protective film forming agent, a silicon wafer with a silicon oxide film having many hydroxyl groups on its surface, and nitriding with few hydroxyl groups It was confirmed that a good water repellency-imparting effect was obtained for both of the silicon wafers with a silicon film, and that cleaning could be performed efficiently.

[Examples 2-3]
The organic solvent used in Example 1 was appropriately changed to perform wafer surface treatment, and further evaluated. The results are shown in Table 1. In Table 1, CTFP / PGMEA means an organic solvent using 1-chloro-3,3,3-trifluoropropene (CTFP) instead of HFE-7100 of Example 1, and DCTFP / PGMEA is It means an organic solvent using cis-1,2-dichloro-3,3,3-trifluoropropene (DCTFP) in place of HFE-7100 in Example 1.

[Example 4]
1 g of butyldimethylsilyldimethylamine [C ₄ H ₉ (CH ₃ ) ₂ SiN (CH ₃ ) ₂ ] as a protective film forming agent, 98.9 g of PGMEA as an organic solvent, and trifluoroacetic acid [CF ₃ COOH] as a catalyst A protective film forming chemical was prepared using 0.1 g. The amount of the catalyst added to the total amount of the protective film forming agent of 100% by mass (hereinafter referred to as catalyst concentration) is 10% by mass. Furthermore, the immersion time of each wafer in the chemical solution for forming the protective film was set to 10 minutes. The rest is the same as the first embodiment.

  As shown in Table 1, the evaluation results of the silicon wafer with the silicon oxide film showed an excellent water repellency-imparting effect with a contact angle of 87 ° after the surface treatment. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.

  On the other hand, as shown in Table 1, the evaluation results of the silicon wafer with the silicon nitride film showed a contact angle after the surface treatment of 71 °, indicating an excellent water repellency imparting effect. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no residue of the water-repellent protective film remained after UV irradiation.

[Examples 5 to 26]
The protective film forming agent, protective film forming agent concentration, catalyst, catalyst concentration, organic solvent, immersion time of each wafer in the protective film forming chemical solution used in Example 4, and each wafer in the protective film forming chemical solution The immersion temperature was changed as appropriate, the wafer was surface-treated, and further evaluated. The results are shown in Table 1. In Table 1, C ₈ H ₁₇ (CH ₃ ) ₂ SiN (CH ₃ ) ₂ means octyldimethylsilyldimethylamine, and C ₈ H ₁₇ Si [N (CH ₃ ) ₂ ] ₃ represents octylsilyl tris. Dimethylamine means (CF ₃ CO) ₂ O means trifluoroacetic anhydride.

[Comparative Example 1]
All were the same as Example 1 except that trimethylchlorosilane [(CH ₃ ) ₃ SiCl]; 1 g was used as the protective film forming agent.

  As shown in Table 1, the evaluation results of the silicon wafer with a silicon oxide film showed a contact angle after the surface treatment of 71 °, indicating an excellent water repellency imparting effect. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.

  On the other hand, as shown in Table 1, the evaluation result of the silicon wafer with a silicon nitride film was 41 ° after the surface treatment, and the water repellency imparting effect was not sufficient.

[Comparative Example 2]
All were the same as in Example 6 except that 1 g of trimethylsilyldimethylamine [(CH ₃ ) ₃ SiN (CH ₃ ) ₂ ]; 1 g was used as the protective film forming agent.

  As shown in Table 1, the evaluation result of the silicon wafer with the silicon oxide film was 91 ° after the surface treatment, indicating an excellent water repellency imparting effect. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no protective film residue remained after UV irradiation.

  On the other hand, as shown in Table 1, the evaluation result of the silicon wafer with the silicon nitride film was that the contact angle after the surface treatment was 60 °, and the water repellency imparting effect was not sufficient.

[Comparative Example 3]
As a protective film forming agent, 1,3-bis (3,3,3-trifluoropropyl) -1,1,3,3-tetramethyldisiloxane silazane _{[[CF 3 (CH 2) 2 (} CH 3) 2 Si ] ₂ NH]; everything was the same as Example 6 except 1 g was used.

As shown in Table 1, the evaluation results of the silicon wafer with the silicon oxide film showed a contact angle after the surface treatment of 96 °, indicating an excellent water repellency imparting effect. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Furthermore, the Ra value of the wafer after UV irradiation was less than 0.5 nm, and it was confirmed that the wafer was not eroded during cleaning, and that no residue of the water-repellent protective film remained after UV irradiation.

  On the other hand, as shown in Table 1, the evaluation result of the silicon wafer with a silicon nitride film was that the contact angle after the surface treatment was 62 °, and the water repellency imparting effect was not sufficient.

  Thus, in the compounds of Comparative Examples 1 to 3, a good water repellency imparting effect was obtained in the case of a silicon wafer with a silicon oxide film having many hydroxyl groups on the surface, but a silicon wafer with a silicon nitride film having few hydroxyl groups on the surface In this case, a sufficient water repellency imparting effect could not be obtained, and the water repellency imparting effect greatly depended on the number of hydroxyl groups depending on the wafer type.

  The protective film forming agent of the present invention, the chemical solution for forming the protective film containing the agent, and the wafer cleaning method using the chemical solution are used for cleaning the surface according to the type of wafer in the field of integrated circuits in the electronics industry. Because it can reduce the change of conditions and the addition of processes, it contributes to the improvement of manufacturing efficiency. Particularly efficient production is possible when dealing with several types of wafers.

DESCRIPTION OF SYMBOLS 1 Wafer 2 Uneven | corrugated pattern on the wafer surface 3 Convex part 4 Pattern concave part 5 Concave width 6 Convex height 7 Convex width 8 Water repellent protective film forming chemical 9 held in the concave part Retained liquid 10 water repellent protective film

Claims (8)

A water-repellent protective film forming agent for forming a protective film on at least the concave surface of the wafer when cleaning a wafer having a concave-convex pattern on the surface and containing silicon element on at least the concave surface of the concave-convex pattern, A water repellent protective film-forming agent, which is a silicon compound represented by the following general formula [ 3 ].

[ Wherein R ² is an unsubstituted or substituted hydrocarbon group having 4 to 18 carbon atoms, and X is a monovalent functional group in which the element bonded to the silicon element is nitrogen, monovalent functional group bonded to an element is oxygen, and a group Ru is selected from a halogen group. ] A water-repellent protective film forming agent for forming a protective film on at least the concave surface of the wafer when cleaning a wafer having a concave-convex pattern on the surface and containing silicon nitride on at least the concave surface of the concave-convex pattern, A water repellent protective film-forming agent, which is a silicon compound represented by the following general formula [ 3 ].

[ Wherein R ² is an unsubstituted or substituted hydrocarbon group having 4 to 18 carbon atoms, and X is a monovalent functional group in which the element bonded to the silicon element is nitrogen, monovalent functional group bonded to an element is oxygen, and a group Ru is selected from a halogen group. ] A chemical solution for forming a water repellent protective film, comprising the water repellent protective film forming agent according to claim 1 . The chemical solution for forming a water-repellent protective film according to claim 3 , comprising an acid. The water-repellent protective film forming agent, characterized in that formed by mixed so that 0.1 to 50 wt% based on 100 mass% of the water repellent protective film forming chemical, claim 3 or The chemical solution for forming a water-repellent protective film according to claim 4 . In the cleaning of a wafer containing a silicon element on at least the concave surface of the concavo-convex pattern in the wafer having the concavo-convex pattern formed on the surface, the steps shown below,
Cleaning the wafer surface with an aqueous cleaning liquid, an aqueous cleaning liquid cleaning step;
A water repellent protective film forming step of holding a water repellent protective film forming chemical in at least the concave portion of the wafer and forming a water repellent protective film on the concave surface;
A liquid removal process for removing liquid on the wafer surface;
Removing the water-repellent protective film from the concave surface, a water-repellent protective film removing step,
A method for cleaning a wafer, comprising using the chemical solution for forming a water-repellent protective film according to any one of claims 3 to 5 in the water-repellent protective film forming step. The method for cleaning a wafer according to claim 6 , wherein the wafer is a wafer containing silicon nitride on at least a concave surface of the concave / convex pattern. The water repellent protective film removing step is at least selected from irradiating the wafer surface with light, heating the wafer, irradiating the wafer surface with plasma, exposing the wafer surface to ozone, and corona discharging the wafer. characterized in that it is carried out in one processing method, the wafer cleaning method according to claim 6 or claim 7.

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