JP5678720B2 - Wafer cleaning method - Google Patents

Description

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

  In the production of semiconductor chips, a fine uneven pattern is formed on the silicon wafer surface through film formation, lithography, etching, etc., and then water (pure water) or an organic solvent is used to clean the wafer surface. Is washed. The elements are in the direction of miniaturization, and the interval between the concave and convex patterns is becoming narrower. For this reason, when washing with water (pure water) and drying the water from the wafer surface, the problem that the concave-convex pattern collapses due to capillary action when the gas-liquid interface passes through the pattern is becoming more likely to occur. . This problem becomes more prominent in semiconductor chips having a line width (recessed portion width) of the order of 20 nm or 10 nm, particularly in the case of a wafer with a pattern of line and space, for example, in which the pattern spacing of the unevenness becomes narrower. ing.

  Patent Document 1 discloses a technique for replacing a cleaning liquid from water to 2-propanol before passing through a gas-liquid interface as a technique for suppressing pattern collapse. However, it is said that there is a limit such that the aspect ratio of the pattern that can be handled is 5 or less.

  Further, Patent Document 2 discloses a technique for a resist pattern as a technique for suppressing pattern collapse. This technique is a technique for suppressing pattern collapse by reducing the capillary force to the limit. However, since the disclosed technique is intended for a resist pattern, it modifies the resist itself, and can be finally removed together with the resist. Therefore, it is necessary to assume a method for removing the treatment agent after drying. Is not applicable to this purpose.

  Further, Patent Document 3 discloses that a wafer surface on which a concavo-convex pattern is formed by a film containing silicon is surface-modified by oxidation or the like, and a water-repellent protective film is formed on the surface using a water-soluble surfactant or silane coupling agent. A cleaning method is disclosed that reduces the capillary force and prevents the pattern from collapsing.

  Patent Documents 4 and 5 disclose techniques for preventing pattern collapse by performing a hydrophobic treatment using a treatment liquid containing a silylating agent such as N, N-dimethylaminotrimethylsilane and a solvent. ing.

JP 2008-198958 A Japanese Patent Laid-Open No. 5-299336 Patent No. 4403202 JP2010-129932A International Publication No. 10/47196 Pamphlet

  The present invention relates to a technique for cleaning a substrate (wafer) for the purpose of improving the manufacturing yield of a device having a circuit pattern that is fine and having a high aspect ratio, particularly in the manufacture of semiconductor devices. The present invention relates to a water-repellent chemical solution and the like intended to improve a cleaning process that easily induces a collapse of a concavo-convex pattern of a wafer having a surface. Until now, a wafer having a silicon element on the surface has been generally used as the wafer. However, with the diversification of patterns, titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, and ruthenium are used. Wafers having at least one substance selected from the group on the surface have begun to be used. 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 surface of the concavo-convex pattern, reaction activity such as hydroxyl groups present on the surface of the concavo-convex pattern or the wafer surface It is necessary to bond the point and the compound forming the protective film. However, in the case of a wafer containing a substance that does not have sufficient reaction active sites, for example, silanol groups, on the surface, such as a wafer having the substance on the surface, any of the treatment liquids and treatment methods described in Patent Documents 3 to 5 are used. Even if it is used, it is impossible to form a water-repellent protective film that prevents pattern collapse.

  The present invention provides a wafer having a concavo-convex pattern formed on the surface, wherein at least a part of the concave surface of the concavo-convex pattern is selected from the group consisting of titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, and ruthenium. A water-repellent protective film (hereinafter sometimes simply referred to as “protective film”) on the concave surface of a wafer containing one substance (hereinafter sometimes referred to as “metal wafer” or simply “wafer”) The metal wafer cleaning method, which improves the cleaning process that easily induces pattern collapse by reducing the interaction between the liquid held in the recess and the surface of the recess, and the protective film A water-repellent protective film-forming chemical (hereinafter referred to as “protective film”) containing a water-repellent protective film-forming agent to be formed (hereinafter sometimes simply referred to as “protective film-forming agent”). Forming chemical "or sometimes simply referred to as" chemical ") and to provide a.

  Pattern collapse occurs when the gas-liquid interface passes through the pattern when the wafer is dried. This is said to be caused by a difference in residual liquid height between a portion where the aspect ratio of the pattern is high and a portion where the aspect ratio is low, thereby causing a difference in capillary force acting on the pattern.

  For this reason, if the capillary force is reduced, it can be expected that the difference in capillary force due to the difference in the residual liquid height will be reduced and the pattern collapse will be eliminated. The magnitude of the capillary force is the absolute value of P obtained by the following formula. From this formula, it is expected that the capillary force can be reduced by reducing γ or cos θ.

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.)

  In the present invention, in order to overcome the above-described problems, attention was paid to a pretreatment method for the surface of a concavo-convex pattern on which a water-repellent protective film is formed and a material for the water-repellent protective film. That is, after forming a reactive site by oxidizing the concave surface of the concave and convex pattern, by forming a water repellent protective film on the concave surface with a water repellent protective film forming agent having a hydrophobic group having strong hydrophobicity, It imparts water repellency to the concave surface.

  The hydrophobic group in the present invention refers to an unsubstituted hydrocarbon group or a hydrocarbon group in which a part of the hydrogen element in the hydrocarbon group is substituted with a halogen element. The hydrophobicity of the hydrophobic group increases as the number of carbon atoms in the hydrocarbon group increases. Furthermore, in the case of a hydrocarbon group in which a part of the hydrogen element in the hydrocarbon group is substituted with a halogen element, the hydrophobicity of the hydrophobic group may increase. In particular, if the halogen element to be substituted is a fluorine element, the hydrophobicity of the hydrophobic group becomes stronger. The greater the number of fluorine elements to be substituted, the stronger the hydrophobicity of the hydrophobic group.

  The present inventors have intensively studied and combined the oxidation treatment and surface treatment with a water-repellent protective film-forming chemical solution containing a silicon compound having a specific hydrophobic group as a water-repellent protective film-forming agent. It was found that a protective film capable of producing good water repellency was formed on the surface of the concavo-convex pattern, and cleaning could be performed efficiently.

The present invention provides a wafer having a concavo-convex pattern formed on the surface, wherein at least a part of the concavo-convex pattern has at least a part of the concave surface selected from the group consisting of titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, and ruthenium. A method for cleaning a wafer containing one kind of substance,
A water repellent protective film forming chemical containing a water repellent protective film forming agent for forming a water repellent protective film on the wafer surface is held in at least a recess of the wafer, wherein the wafer surface is oxidized. A method for cleaning a wafer comprising a water repellent protective film forming step of forming a water repellent protective film on the concave surface, wherein the water repellent protective film forming agent is a silicon compound represented by the following general formula [1] It is.
R ¹ _a SiX _4-a [1]
[In the formula [1], each R ¹ is independently of each other hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group in which a hydrogen element is substituted with a halogen element, and the formula [1] The total number of carbon atoms contained in R ¹ is 6 or more, X is independently of each other a monovalent functional group in which the element bonded to the silicon element is nitrogen, and the element bonded to the silicon element is oxygen It is at least one group selected from the group consisting of a certain monovalent functional group and a halogen group, and a is an integer of 1 to 3. ]

The water repellent protective film forming agent is preferably a silicon compound represented by the following general formula [2].
R ¹ ₃ SiX [2]
[In the formula [2], each R ¹ is independently of each other hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group in which a hydrogen element is substituted with a halogen element, and the formula [2] The total number of carbon atoms contained in R ¹ is 6 or more, X is a monovalent functional group in which the element bonded to the silicon element is nitrogen, and monovalent functional group in which the element bonded to the silicon element is oxygen Or a halogen group. ]

In addition, the water repellent protective film forming agent is preferably a silicon compound represented by the following general formula [3].
R ² (CH ₃ ) ₂ SiX [3]
[In the formula [3], R ² is an unsubstituted hydrocarbon group having 4 to 18 carbon atoms, or a hydrogen group in which a hydrogen element is substituted with a halogen element, and X is a monovalent element in which an element bonded to a silicon element is nitrogen A monovalent functional group in which the element bonded to the silicon element is oxygen, or a halogen group. ]

In addition, the water repellent protective film forming agent is preferably a silicon compound represented by the following general formula [4].
R ³ (CH ₃ ) ₂ SiX [4]
[In the formula [4], R ³ is a hydrocarbon group in which at least a part of hydrogen atoms having 4 to 18 carbon atoms is substituted with a fluorine element, and X is a monovalent element in which an element bonded to a silicon element is nitrogen A monovalent functional group in which the element bonded to the silicon element is oxygen, or a halogen group. ]

  In the oxidation treatment, the wafer is preferably immersed in an oxidation treatment solution.

  The oxidation treatment liquid used in the oxidation treatment is preferably at least one treatment liquid selected from the group consisting of a treatment liquid containing ozone, a treatment liquid containing hydrogen peroxide, and a treatment liquid containing acid.

Further, the present invention is a water repellent protective film forming chemical used in the above-described wafer cleaning method, which contains a water repellent protective film forming chemical represented by the following general formula [1]. is there.
R ¹ _a SiX _4-a [1]
[In the formula [1], each R ¹ is independently of each other hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group in which a hydrogen element is substituted with a halogen element, and the formula [1] The total number of carbon atoms contained in R ¹ is 6 or more, X is independently of each other a monovalent functional group in which the element bonded to the silicon element is nitrogen, and the element bonded to the silicon element is oxygen And at least one group selected from the group consisting of a monovalent functional group and a halogen group, a is an integer of 1 to 3. ]

The water repellent protective film forming agent is preferably a silicon compound represented by the following general formula [2].
R ¹ ₃ SiX [2]
[In the formula [2], each R ¹ is independently of each other hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group in which a hydrogen element is substituted with a halogen element, and the formula [2] The total number of carbon atoms contained in R ¹ is 6 or more, X is a monovalent functional group in which the element bonded to the silicon element is nitrogen, and monovalent functional group in which the element bonded to the silicon element is oxygen Or a halogen group. ]

In addition, the water repellent protective film forming agent is preferably a silicon compound represented by the following general formula [3].
R ² (CH ₃ ) ₂ SiX [3]
[In the formula [3], R ² is an unsubstituted hydrocarbon group having 4 to 18 carbon atoms, or a hydrogen group in which a hydrogen element is substituted with a halogen element, and X is a monovalent element in which an element bonded to a silicon element is nitrogen A monovalent functional group in which the element bonded to the silicon element is oxygen, or a halogen group. ]

In addition, the water repellent protective film forming agent is preferably a silicon compound represented by the following general formula [4].
R ³ (CH ₃ ) ₂ SiX [4]
[In the formula [4], R ³ is a hydrocarbon group in which at least a part of hydrogen atoms having 4 to 18 carbon atoms is substituted with a fluorine element, and X is a monovalent element in which an element bonded to a silicon element is nitrogen A monovalent functional group in which the element bonded to the silicon element is oxygen, or a halogen group. ]

  The water repellent protective film forming chemical solution preferably contains a solvent.

  The water repellent protective film forming chemical preferably contains an acid.

  Moreover, it is preferable that 0.1-50 mass% of said water-repellent protective film forming agents are contained in 100 mass% of total amounts of water-repellent protective film forming chemicals.

  In the present invention, the water-repellent protective film is a film that is formed on the wafer surface to lower the wettability of the wafer surface, that is, a film that imparts water repellency. In the present invention, the water repellency means that the surface energy of the article surface is reduced and the interaction (for example, hydrogen bond, intermolecular force) between water or other liquid and the article surface is reduced. It is. In particular, the effect of reducing the interaction with water is great, but it has the effect of reducing the interaction with a mixed liquid of water and a liquid other than water or a liquid other than water. By reducing the interaction, the contact angle of the liquid with the article surface can be increased.

  By using the wafer cleaning method of the present invention and a chemical solution, at least a part of the concave surface of the concave / convex pattern on the surface is formed of titanium, titanium nitride, tungsten, aluminum, copper, tin, In the process of cleaning a wafer containing at least one substance selected from the group consisting of tantalum nitride and ruthenium, the capillary force acting on the concavo-convex pattern is reduced, and the pattern collapse preventing effect is exhibited. When this cleaning method is used, the cleaning step in the method for manufacturing a wafer having a concavo-convex pattern on the surface can be improved without lowering the throughput. Therefore, the cleaning method of the present invention and the method of manufacturing a wafer having a concavo-convex pattern on the surface performed using a chemical solution are highly productive.

  The cleaning method and the chemical solution of the present invention can cope with a concavo-convex pattern having an aspect ratio of, for example, 7 or more, which is expected to become higher in the future, and can reduce the cost of production of higher-density semiconductor devices. To do. In addition, the conventional apparatus can be applied without significant change, and as a result, can be applied to the manufacture of various semiconductor devices.

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 protective film formation chemical | medical solution 8. FIG. It is a figure which shows the schematic diagram of the state by which the liquid was hold | maintained at the recessed part 4 in which the protective film was formed.

In general, before the wafer cleaning method of the present invention is performed, the following pre-steps are often performed.
A pattern forming process in which the wafer surface is a surface having a fine uneven pattern;
Pretreatment comprising at least one selected from the group consisting of water, an organic solvent, a mixed solution of water and an organic solvent, and a mixed solution in which at least one of hydrogen peroxide, ozone, acid, and alkali is mixed. to clean the wafer surface with a cleaning solution, as precleaning Engineering.

  In the pattern forming step, the method is not limited as long as a fine pattern can be formed on the wafer surface. As a general method, after applying a resist to the wafer surface, the resist is exposed through a resist mask. Then, a resist having a desired concavo-convex pattern is produced by etching away the exposed resist or the resist that has not been exposed. 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 concave portion of the resist pattern is selectively etched. Finally, when the resist is removed, a wafer having a fine uneven pattern is obtained.

In addition, as the wafer, the surface of a silicon wafer, a wafer composed of a plurality of components including silicon and / or silica (SiO ₂ ), a silicon carbide wafer, a sapphire wafer, various compound semiconductor wafers, a plastic wafer, etc. is made of titanium, A multilayer film is formed on a wafer coated with a metal material layer of titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, and ruthenium, and at least one of the layers is formed of the metal material. The above-mentioned concavo-convex pattern forming step is performed in a layer including a layer of the metal-based substance. Moreover, when the said uneven | corrugated pattern is formed, the thing in which at least one part of this uneven | corrugated pattern becomes this metal-type substance is also contained. Furthermore, the thing which formed the uneven | corrugated pattern on the wafer and formed the layer of the said metal-type substance on the surface of the uneven | corrugated pattern is also included.

  In addition, the protective film can be formed on the surface of the metal-based material even on a wafer composed of a plurality of components including the metal-based material. As a wafer composed of the plurality of components, the metal-based material is formed on the wafer surface, or when a concavo-convex pattern is formed, at least a part of the concavo-convex pattern becomes the metal-based material. Also included. In addition, it is at least the surface of the said metal-type substance part in the said uneven | corrugated pattern that can form a protective film with the chemical | medical solution of this invention.

  Examples of the cleaning liquid used in the pre-cleaning step include water, an organic solvent, a mixed liquid of water and an organic solvent, and a mixed liquid in which at least one of hydrogen peroxide, ozone, acid, and alkali is mixed. At least one selected from the group consisting of: In addition, cleaning may be performed by sequentially replacing a plurality of types of cleaning liquids among the above cleaning liquids.

In the cleaning of the wafer after the formation of the concavo-convex pattern, the resist is removed, after removing the particles and the like of the wafer surface, in removing by Riarai solution purification to drying, the width of the recess is small, the convex portion If the aspect ratio is large, pattern collapse tends to occur. The concavo-convex pattern is defined as shown in FIGS. FIG. 1 is a schematic view when a wafer 1 whose surface has a concavo-convex pattern 2 is viewed from the perspective, and FIG. 2 shows a part of an aa ′ cross section in FIG. 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.

The wafer cleaning method of the present invention comprises:
A water repellent protective film forming chemical solution containing a water repellent protective film forming agent for forming a water repellent protective film on the wafer surface is held in at least the recesses of the wafer, and an oxidation treatment step for oxidizing the wafer surface. A water-repellent protective film forming step of forming a water-repellent protective film on the concave surface;

  In the oxidation process, the wafer surface is oxidized. In the cleaning method of the present invention, in a wafer having a concavo-convex pattern formed on the surface, at least a part of the concave surface of the concavo-convex pattern is selected from the group consisting of titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, and ruthenium. A wafer containing at least one selected substance is targeted, and at least a portion made of the substance on the wafer surface is oxidized. By this oxidation, a hydroxyl group is formed on the surface of the substance, and it becomes possible to react the hydroxyl group with a water-repellent protective film-forming chemical used in a water-repellent protective film-forming step which is a later step.

  In the wafer cleaning method of the present invention, in order to efficiently perform the cleaning without causing pattern collapse, the water repellent protective film forming step from the oxidation treatment step is performed in a state where liquid is always held in at least the concave portion of the wafer. It is preferable to carry out with. Further, when the pre-cleaning step is performed, it is preferable to perform the water-repellent protective film forming step from the pre-cleaning step in a state where the liquid is always held in at least the concave portion of the wafer. In addition, when the water-repellent protective film forming chemical liquid 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 oxidation treatment 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. The form of the chemical solution or cleaning liquid when supplying the oxidation treatment liquid, the chemical solution, or other liquid to at least the concave portion of the concave / convex pattern of the wafer is not particularly limited as long as it becomes liquid when held in the concave portion. For example, there are liquid, vapor and the like.

  The oxidation of the wafer surface in the oxidation treatment step is not particularly limited as long as the wafer surface can be oxidized, but it is preferable to use a method of holding an oxidation treatment liquid on the wafer surface. The method of holding the oxidation treatment liquid on the wafer surface includes a method of supplying and pouring liquid around the rotation center while rotating the wafer in the case of a single wafer method, and in the oxidation treatment solution in the case of a batch method. The method of immersing is mentioned. Further, when at least one treatment liquid selected from the group consisting of a treatment liquid containing ozone, a treatment liquid containing hydrogen peroxide, and a treatment liquid containing acid is used as the oxidation treatment liquid, these oxidation treatment liquids are powerful. Therefore, it is possible to suitably oxidize at least one substance selected from the group consisting of titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, and ruthenium on the wafer surface. .

  The oxidation treatment step may be performed using a normal temperature oxidation treatment solution or an oxidation treatment solution heated to 30 to 200 ° C. In general, metals and nitrides tend to be oxidized at higher temperatures, and it is preferable to treat the oxidation treatment solution by heating to 30 to 200 ° C. When the treatment is carried out using an oxidation treatment solution at 100 ° C. or higher, the treatment solution will boil if most of the treatment solution consists of water, so that the temperature cannot be raised at normal pressure. For this reason, when the treatment is performed using an oxidation treatment solution at 100 ° C. or higher, it is preferable to use a solvent different from water.

  Next, the water repellent protective film forming step will be described. The transition from the oxidation treatment step to the water repellent protective film forming step is performed by replacing the oxidation treatment liquid held in at least the concave portion of the concave / convex pattern of the wafer in the oxidation treatment step with a water repellent protective film forming chemical solution. Is called. In the replacement of the oxidation treatment liquid with the water-repellent protective film forming chemical liquid, it may be directly replaced, or after being replaced at least once with a different cleaning liquid A (hereinafter sometimes simply referred to as “cleaning liquid A”). Alternatively, a water repellent protective film forming chemical solution 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 at least in the concave portions 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 water repellent protective film forming chemical 8. 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, the water repellent protective film forming chemical 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 at least in 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.

  In the water-repellent protective film forming step, if the temperature of the chemical solution is increased, the protective film can be easily formed in a shorter time. However, the stability of the chemical solution is impaired by boiling or evaporation of the water-repellent protective film-forming chemical solution. Since there exists a possibility, it is preferable that the said chemical | medical solution is hold | maintained at 10-160 degreeC, and 15-120 degreeC is especially preferable.

Subsequently, the water-repellent protective film forming chemical used in the water-repellent protective film forming step will be described. The chemical solution contains a water repellent protective film forming agent represented by the following general formula [1].
R ¹ _a SiX _4-a [1]
[In the formula [1], each R ¹ is independently of each other hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group in which a hydrogen element is substituted with a halogen element, and the formula [1] The total number of carbon atoms contained in R ¹ is 6 or more, X is independently of each other a monovalent functional group in which the element bonded to the silicon element is nitrogen, and the element bonded to the silicon element is oxygen Is at least one group selected from the group consisting of a monovalent functional group and a halogen group, and a is an integer of 1 to 3. ]

For example, the silicon oxide surface obtained by oxidizing the silicon surface has abundant hydroxyl groups that are reactive sites, but in general, titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, In addition, the above-described oxidation treatment is performed on the surface of ruthenium and ruthenium, and the amount of hydroxyl groups is less than that on the surface of silicon oxide even on the surfaces of titanium oxide, tungsten oxide, aluminum oxide, copper oxide, tin oxide, tantalum oxide, and ruthenium oxide. . Even if a conventional silane coupling agent is reacted with this small number of hydroxyl groups, it is difficult to impart sufficient water repellency to the surface. However, if the hydrophobic group is a group having stronger hydrophobicity, sufficient water repellency can be imparted. If the total number of carbon atoms in R ¹ is large, that is, R ¹ is a hydrophobic group having stronger hydrophobicity, and R ¹ is a part of or all of hydrogen elements substituted with halogen elements. It may be a hydrocarbon group. In particular, if the water repellent protective film forming agent having a hydrophobic group having a strong hydrophobicity with a total carbon number of R ¹ of 6 or more, even if there are few hydroxyl groups present on the wafer surface, sufficient water repellent performance Can be formed. Note that the total number of carbons contained in R ¹ of the formula [1] is 6 or more means that the total number of all carbons of the hydrophobic group contained in the formula [1] as 1 to 3 as R ¹ It shows that it is 6 or more.

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, iodine, etc., any functional group may be used, for example, —NSi (CH ₃ ) ₃ group, —NSi (CH ₃ ) ₂ C ₄ H ₉ group, —NSi (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, iodine, etc., as long as it is a functional group composed of, 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.

  The group represented by X in the general formula [1] reacts with a hydroxyl group on the wafer surface to form a bond between the silicon element in the silicon compound and the wafer surface, thereby forming a protective film. Can be 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 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, _{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 S _{N (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, _{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 (C _{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 _{6 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 _{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 Aminosilane compounds such as 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 Can be mentioned.

Further, a in the general formula [1] may be an integer of 1 to 3, but when a is 1 or 2, when the chemical solution is stored for a long period of time, a polymerization reaction between the silicon compounds occurs due to water mixing. Tends to occur, and it tends to be difficult to stably form a water-repellent protective film on the wafer surface. Considering this, a compound of formula (1) where a is 3, that is, a silicon compound represented by the following formula (2) is preferable.
R ¹ ₃ SiX [2]
[In Formula [2], each R ¹ is independently of each other hydrogen or a hydrocarbon group having 1 to 18 carbon atoms which is unsubstituted or substituted with a halogen element, and in R ^{1 of} Formula [2], The total number of carbon atoms contained is 6 or more, and X is 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, or a halogen group It is. ]

Further, in the silicon compound in which a in the general formula [1] is 3, one R ¹ is an unsubstituted hydrocarbon group having 4 to 18 carbon atoms or a hydrocarbon group substituted with a halogen element, 2 A compound in which each R ¹ is a methyl group, that is, a silicon compound represented by the following general formula [3] is preferable because of its high reactivity with the hydroxyl group on the wafer surface. This is because the steric hindrance due to the hydrophobic group greatly affects the reactivity in the reaction between the hydroxyl group on the wafer surface and the group represented by X of the silicon compound. This is because the remaining two except the longest one are preferably shorter.
R ² (CH ₃ ) ₂ SiX [3]
[In the formula [3], 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, A monovalent functional group in which the element bonded to the silicon element is oxygen or a halogen group. ]

In the silicon compound represented by the general formula [1], one R ¹ is a hydrocarbon group in which at least a part of hydrogen atoms having 4 to 18 carbon atoms is substituted with a fluorine element, It is preferable that all of R ¹ is a methyl group, that is, a silicon compound represented by the following general formula [4] because excellent water repellency can be imparted to the wafer surface. Since the hydrocarbon group in which at least a part of the hydrogen element is substituted with the fluorine element as described above is a hydrophobic group having particularly strong hydrophobicity, as a result, excellent water repellency can be imparted to the resulting protective film.
R ³ (CH ₃ ) ₂ SiX [4]
[In the formula [4], R ³ is a hydrocarbon group in which at least a part of hydrogen atoms having 4 to 18 carbon atoms is substituted with a fluorine element, and X is a monovalent element in which the element bonded to the silicon element is nitrogen. The functional group, a monovalent functional group in which the element bonded to the silicon element is oxygen, or a halogen group. ]

  The water-repellent protective film forming agent may be contained at least in the water-repellent protective film-forming chemical solution, and can be diluted using various organic solvents. The organic solvent only needs to dissolve the water-repellent protective film forming agent. For example, hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide solvents, alcohols, polyhydric alcohols. And derivatives thereof, nitrogen-containing compound solvents and the like are preferably used. When water is used as the solvent to be diluted, the group represented by X of the silicon compound is hydrolyzed with water to form a silanol group (Si—OH), and the generated silanol groups undergo a condensation reaction to form the silicon. The compounds combine to form a dimer. Since this dimer has low reactivity with the hydroxyl group on the wafer surface, the wafer surface cannot be made sufficiently water-repellent or the time required for water-repelling becomes longer, so it is preferable to use water as a solvent. Absent.

  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 on the wafer surface 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), methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, Asahi Hydrofluoroethers such as Clin AE-3000 (manufactured by Asahi Glass), Novec HFE-7100, Novec HFE-7200, Novec7300, and Novec7600 (all manufactured by 3M), chlorocarbons such as tetrachloromethane, hydrochlorocarbons such as chloroform, dichloro Chlorofluorocarbons such as difluoromethane, 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3- Hydrochlorofluorocarbons such as chloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene Examples of the sulfoxide solvent include dimethyl sulfoxide, and examples of the polyhydric alcohol derivative having no hydroxyl group include diethylene glycol monoethyl ether acetate, ethylene glycol, and the like. Examples of nitrogen-containing compound solvents having no N—H bond include monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like. Te is, N, N- dimethylformamide, N, N- dimethylacetamide, N- methyl-2-pyrrolidone, triethylamine, pyridine and the like.

  Furthermore, if a nonflammable organic solvent is used, the water repellent protective film forming chemical solution becomes nonflammable, or the flash point becomes high, and the risk of the water repellent protective film protective film forming chemical solution decreases. This is preferable. Many halogen-containing solvents are nonflammable, and the nonflammable halogen-containing solvent can be suitably used as a nonflammable organic solvent.

  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.

  The water-repellent protective film forming chemical is preferably contained in an amount of 0.1 to 50% by mass of the water-repellent protective film-forming agent in a total amount of 100% by mass of the chemical. Is 0.3 to 20% by mass with respect to 100% by mass of the total amount of the chemical solution. If the water-repellent protective film forming agent is less than 0.1% by mass, the effect of imparting water repellency tends to be insufficient, and if it exceeds 50% by mass, components derived from the water-repellent protective film forming agent are impurities on the wafer surface after cleaning. As such, there is a concern that it remains as such. Moreover, since the usage-amount of a water repellent protective film formation agent increases, it is unpreferable also from a cost viewpoint.

  Further, a catalyst may be added to the chemical solution in order to promote the reaction between the silicon compound and the hydroxyl group on the wafer surface. Examples of such catalysts include trifluoroacetic acid, trifluoroacetic anhydride, pentafluoropropionic acid, pentafluoropropionic anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, sulfuric acid, hydrogen chloride-free acid, ammonia, and the like. Bases such as alkylamines, aprotic nitrogen-containing solvents such as pyridine and dimethylformamide, salts such as ammonium sulfide, potassium acetate and methylhydroxyamine hydrochloride, and metal complexes and metal salts such as tin, aluminum and titanium Preferably used. 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. The catalyst may form a part of the water-repellent protective film by reaction.

In particular, when the number of carbon atoms of the hydrophobic group R ¹ of the silicon compound represented by the general formula [1] increases, the reactivity of the silicon compound with respect to the hydroxyl group on the wafer surface may decrease due to steric hindrance. In this case, by adding an acid not containing water as a catalyst, the reaction between the hydroxyl group on the wafer surface and the silicon compound is promoted to compensate for the decrease in reactivity due to the steric hindrance of the hydrophobic group as described above. 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. Furthermore, there is a concern that the impurities may remain on the wafer surface as impurities. For this reason, 0.01-100 mass% of the said catalyst addition amount is preferable, More preferably, it is 0.1-50 mass%, More preferably, it is 0.2-20 mass%.

  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 agent. The wafer in the schematic diagram of FIG. 4 shows a part of the a-a ′ cross section of FIG. 1. A water repellent protective film 10 is formed on the surface of the recess 4 by a water repellent protective film forming agent. 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 (a mixed solution of a chemical solution and a cleaning solution) 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 alcohol derivatives, And nitrogen-containing compound solvents.

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 as described above.
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 when it is assumed that water is held on the surface is preferably 50 to 130 ° 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. For example, in the case of a line-and-space pattern wafer with a line width (width of recess) of 45 nm, the capillary force is preferably 2.1 MN / m ² or less. It is preferable that the capillary force is 2.1 MN / m ² or less because pattern collapse hardly occurs. Further, when the capillary force becomes small, pattern collapse hardly occurs. Therefore, the capillary force is particularly preferably 1.1 MN / m ² or less. Furthermore, it is ideal to adjust the contact angle with the cleaning liquid to around 90 ° so that the capillary force is as close to 0.0 MN / m ² as possible.

Subsequently, a method for removing the liquid held in the concave portion of the wafer after being cleaned by the wafer cleaning method of the present invention 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. 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 addition, in order to efficiently remove the liquid, the remaining liquid may be dried after the retained liquid is drained and removed.

  Finally, a method for removing the water repellent protective film from the wafer surface after removing the liquid 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 is preferably used. Further, the wafer may be heated while irradiating light.

  When the wafer is heated, the wafer is heated 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 Therefore, in the present invention, the evaluation was mainly performed on the protective film forming chemical solution. Also, 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 apparent from FIG. 5, the pattern collapse greatly depends on the contact angle of the cleaning liquid to the wafer surface, that is, the contact angle of the liquid droplets, and the surface tension of the cleaning liquid. In the case of the cleaning liquid held in the concave portion of the concave / convex pattern, the contact angle of the droplet and the capillary force acting on the concave portion, which may be considered equivalent to the pattern collapse, have a correlation. Capillary force may be derived from the evaluation of the contact angle of the drop. In the examples, water was used as the cleaning liquid.

  However, in the case of a wafer having a fine uneven pattern on the surface, the contact angle of the protective film 10 itself formed on the surface of the uneven pattern cannot be accurately evaluated.

  As described in JIS R 3257 “Test method for wettability of substrate glass surface”, water droplet contact angle is 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 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, a wafer with a titanium nitride film having a titanium nitride layer on a silicon wafer with a smooth surface (hereinafter sometimes referred to as “TiN wafer”) was used as the wafer with a smooth surface.

  Details are described below. Below, the evaluation method of the wafer cleaned by the cleaning method of the present invention, the preparation of the protective film forming chemical solution, and the evaluation result of the wafer cleaned by the cleaning method of the present invention will be described.

[Evaluation method of wafer cleaned by cleaning method of the present invention]
As evaluation methods for wafers cleaned by the cleaning method of the present invention, the following evaluations (1) to (4) were performed.

(1) Contact angle evaluation of the protective film formed on the wafer surface About 2 μl of pure water is placed on the surface of the wafer on which the protective film is formed, and the angle (contact angle) formed between the water droplet and the wafer surface is measured by a contact angle meter (Kyowa). It was measured by Interface Science: CA-X type). Here, the protective film having a contact angle in the range of 50 to 130 ° was regarded as acceptable.

(2) Evaluation of capillary force P was calculated using the following equation, and the capillary force (absolute value of P) was determined.
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.)
In the present embodiment, as an example of the pattern shape, a line-and-space pattern wafer having a line width (recessed portion width) of 45 nm is assumed. In the pattern with a line width of 45 nm, when the gas-liquid interface passes through the pattern on the wafer surface, the pattern tends to collapse when the liquid is water, and the pattern does not easily collapse when the liquid is 2-propanol. When the wafer surface is, for example, titanium nitride, the contact angle of 2-propanol with the surface is 0.5 °, and the contact angle of water is 2 °. The same applies to other metal substances (titanium, tungsten, aluminum, copper, tin, tantalum nitride, ruthenium, etc.). In the case of the above conditions, when the cleaning liquid is 2-propanol (surface tension: 22 mN / m), the capillary force is 0.98 MN / m ² . On the other hand, the capillary force is 3.2 MN / m ^{2 in} water (surface tension: 72 mN / m) having the largest surface tension among liquids excluding mercury. Therefore, the target was 2.1 MN / m ^{2 in the} middle, and the test was accepted if the capillary force when water was retained was 2.1 MN / m ² or less.

(3) Removability of protective film The sample was irradiated with UV light from a low-pressure mercury lamp for 1 minute under the following conditions. When the contact angle of water droplets was 10 ° or less after irradiation, it was judged that the protective film was removed, and the result was accepted.
・ Lamp: Sen Special Light Source PL2003N-10
Illuminance: 15 mW / cm ² (distance from light source to sample is 10 mm)

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。 (4) Evaluation of surface smoothness of wafer after removal of protective film Surface observation with an atomic force electron microscope (Seiko-Electronics: SPI3700, 2.5 μm square scan) and centerline average surface roughness of the surface before and after wafer cleaning : Ra (nm) difference ΔRa (nm) was determined. Ra is a three-dimensional extension of the centerline average roughness defined in JIS B 0601 to the measurement surface. “The absolute value of the deviation from the reference surface to the specified surface is averaged. The value was calculated by the following formula.

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.

  The Ra value of the wafer surface before forming the protective film and the Ra value of the wafer surface after removing the protective film are measured. If the difference (ΔRa) is within ± 1 nm, the wafer surface is eroded by cleaning. It was determined that there was no residue of the chemical solution on the wafer surface, and the test was accepted.

[Example 1]
(1) Preparation of water repellent protective film-forming chemical solution Nonafluorohexyldimethylchlorosilane [C ₄ F ₉ (CH ₂ ) ₂ (CH ₃ ) ₂ SiCl] as a water repellent protective film forming agent; 10 g, hydrofluoroether ( 3M HFE-7100); 90 g was mixed and stirred for about 5 minutes, and the concentration of the protective film forming agent relative to the total amount of the protective film forming chemical (hereinafter referred to as “protective film forming agent concentration”) was 10% by mass. A protective film forming chemical was obtained.

(2) Pre-cleaning of TiN wafer As pre-cleaning, a wafer with a smooth titanium nitride film (a silicon wafer having a titanium nitride layer with a thickness of 50 nm on the surface) was immersed in a 1% by mass hydrofluoric acid aqueous solution for 2 minutes, and then purified. Immerse in water for 1 minute.

(3) Oxidation treatment of TiN wafer Hydrochloric acid is mixed in a solvent in which water / ethylene glycol (hereinafter referred to as “EG”) is mixed at a mass ratio of 20/80 so that the concentration is 0.1 mol / L. Then, an oxidation treatment solution was prepared. The TiN wafer after the “(2) TiN wafer pretreatment step 2” was immersed in the oxidation treatment liquid maintained at 130 ° C. for 1 minute to carry out an oxidation treatment.

(4) Surface treatment with water-repellent protective film forming chemical on the wafer surface The TiN wafer after “(3) TiN wafer oxidation treatment” is 1 in 2-propanol (hereinafter sometimes referred to as “iPA”). Then, it was immersed in propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as “PGMEA”) for 1 minute. Thereafter, as a water repellent protective film forming step, the TiN wafer was immersed in the protective film forming chemical solution prepared in the above “(1) Preparation of protective film forming chemical solution” at 20 ° C. for 1 minute. Thereafter, the TiN wafer was immersed in iPA for 1 minute, and then immersed in pure water for 1 minute. In addition, the process after the said pre-processing process 2 was performed in the state by which the liquid was always hold | maintained on the TiN wafer surface. Finally, the TiN wafer was taken out from the pure water and air was blown to remove the pure water on the surface of the TiN wafer.

When the obtained TiN wafer was evaluated in the manner described in “Method for evaluating wafer cleaned by the cleaning method of the present invention”, the initial contact angle before forming the water-repellent protective film was less than 10 °. The contact angle after the formation of the protective film was 96 °, indicating an excellent water repellency imparting effect. Further, when the capillary force when water was retained was calculated using the formula described in the above “Evaluation of Capillary Force”, the capillary force was 0.3 MN / m ² and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Further, the ΔRa value of the wafer by UV irradiation was within ± 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.

[Example 2]
Octyldimethyldimethylaminosilane [C ₈ H ₁₇ (CH ₃ ) ₂ SiN (CH ₃ ) ₂ ] as a water repellent protective film forming agent; 5 g, PGMEA as an organic solvent; 94.82 g, trifluoroacetic anhydride as a catalyst [(CF ₃ CO) ₂ O]; 0.18 g was mixed and stirred for about 5 minutes to obtain a protective film-forming chemical solution having a protective film-forming agent concentration of 5 mass%.

  The TiN wafer subjected to “(2) TiN wafer pre-cleaning” and “(3) TiN wafer oxidation treatment” as in Example 1 was immersed in iPA for 1 minute, and then immersed in PGMEA for 1 minute. Then, as a water-repellent protective film forming step, it was immersed in the protective film-forming chemical solution prepared above at 45 ° C. for 1 hour. Thereafter, the TiN wafer was immersed in iPA for 1 minute, and then immersed in pure water for 1 minute. In addition, the process after the said pre-processing process 2 was performed in the state by which the liquid was always hold | maintained on the TiN wafer surface. Finally, the TiN wafer was taken out from the pure water and air was blown to remove the pure water on the surface of the TiN wafer.

When the obtained TiN wafer was evaluated in the manner described in “Method for evaluating wafer cleaned by the cleaning method of the present invention”, the initial contact angle before forming the water-repellent protective film was less than 10 °. The contact angle after the formation of the protective film was 71 °, indicating an excellent water repellency imparting effect. Further, when the capillary force when water was retained was calculated using the formula described in the above “Evaluation of Capillary Force”, the capillary force was 1.0 MN / m ² and the capillary force was small. Moreover, the contact angle after UV irradiation was less than 10 °, and the protective film could be removed. Further, the ΔRa value of the wafer by UV irradiation was within ± 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.

[Comparative Example 1]
5 g of N, N-dimethylaminotrimethylsilane [(CH ₃ ) ₃ SiN (CH ₃ ) ₂ ]; 5 g and PGMEA; 95 g as an organic solvent were mixed as a water-repellent protective film forming agent, and stirred for about 5 minutes to form a protective film A protective film forming chemical solution having a forming agent concentration of 5% by mass was obtained. The TiN wafer subjected to “(2) TiN wafer pretreatment step 2” and “(3) TiN wafer oxidation treatment” in the same manner as in Example 1 was immersed in iPA for 1 minute, and then in PGMEA for 1 minute. After soaking, as a water-repellent protective film forming step, the film was immersed in the protective film-forming chemical solution prepared above for 1 hour at 20 ° C. Thereafter, the TiN wafer was immersed in iPA for 1 minute, and then immersed in pure water for 1 minute. In addition, the process after the said pre-processing process 2 was performed in the state by which the liquid was always hold | maintained on the TiN wafer surface. Finally, the TiN wafer was taken out from the pure water and air was blown to remove the pure water on the surface of the TiN wafer.

When the obtained TiN wafer was evaluated in the manner described in “Method for evaluating wafer cleaned by the cleaning method of the present invention”, the initial contact angle before forming the water-repellent protective film was less than 10 °. The contact angle after forming the protective film was also 23 °, and sufficient water repellency could not be imparted. Further, when the capillary force when water was retained was calculated using the formula described in the above “Evaluation of Capillary Force”, the capillary force was 2.9 MN / m ² and the capillary force was large.

[Comparative Example 2]
5 g of N, N-dimethylaminotrimethylsilane [(CH ₃ ) ₃ SiN (CH ₃ ) ₂ ]; 5 g and PGMEA; 95 g as an organic solvent were mixed as a water-repellent protective film forming agent, and stirred for about 5 minutes to form a protective film A protective film forming chemical solution having a forming agent concentration of 5% by mass was obtained. After performing “(2) TiN wafer pre-cleaning” in the same way as in Example 1, without performing “(3) TiN wafer oxidation treatment”, the TiN wafer was immersed in iPA for 1 minute, and then PGMEA. After being immersed for 1 minute, as a water-repellent protective film forming step, it was immersed in the protective film-forming chemical solution prepared above at 20 ° C. for 1 hour. Thereafter, the TiN wafer was immersed in iPA for 1 minute, and then immersed in pure water for 1 minute. In addition, the process after the said pre-processing process 2 was performed in the state by which the liquid was always hold | maintained on the TiN wafer surface. Finally, the TiN wafer was taken out from the pure water and air was blown to remove the pure water on the surface of the TiN wafer.

When the obtained TiN wafer was evaluated in the manner described in “Method for evaluating wafer cleaned by the cleaning method of the present invention”, the initial contact angle before forming the water-repellent protective film was less than 10 °. The contact angle after forming the protective film was 18 °, and sufficient water repellency could not be imparted. Moreover, when the capillary force when water was held was calculated using the formula described in the above “Evaluation of Capillary Force”, the capillary force was 3.0 MN / m ² and the capillary force was large.

DESCRIPTION OF SYMBOLS 1 Wafer 2 Convex / concave pattern on 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 concave part 4 Retained in concave part 4 Liquid 10 water repellent protective film

Claims (4)

In the cleaning method of drying after forming a water-repellent protective film on a wafer having a concavo-convex pattern formed on the surface , the wafer has at least a part of the concave surface of the concavo-convex pattern made of titanium, titanium nitride, tungsten, aluminum, copper, tin, a web c comprising at least one material selected from the group consisting of tantalum nitride, and ruthenium,
Pretreatment comprising at least one selected from the group consisting of water, an organic solvent, a mixed solution of water and an organic solvent, and a mixed solution in which at least one of hydrogen peroxide, ozone, acid, and alkali is mixed. A pre-cleaning step of cleaning the wafer surface with a cleaning liquid; at least one selected from the group consisting of ozone, hydrogen peroxide and acid on the wafer surface ; water; and a boiling point higher than 100C An oxidation treatment liquid containing a solvent other than water is held at 100 to 200 ° C. to oxidize the wafer surface to form a hydroxyl group on the wafer surface . Oxidation treatment step A water repellent protective film is formed on the wafer surface A water-repellent protective film-forming chemical solution containing a water-repellent protective film-forming chemical solution for holding a water-repellent protective film on at least the concave portion of the wafer and forming a water-repellent protective film on the concave surface, Repellent Sexual protective film forming agent, characterized in that it is a silicon compound represented by the following general formula [1], the method of cleaning the wafer.
R ¹ _a SiX _4-a [1]
[In the formula [1], each R ¹ is independently of each other hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group in which a hydrogen element is substituted with a halogen element, and the formula [1] The total number of carbon atoms contained in R ¹ is 6 or more, X is independently of each other a monovalent functional group in which the element bonded to the silicon element is nitrogen, and the element bonded to the silicon element is oxygen And at least one group selected from the group consisting of a monovalent functional group and a halogen group, a is an integer of 1 to 3. ] The method for cleaning a wafer according to claim 1, wherein the water repellent protective film forming agent is a silicon compound represented by the following general formula [2].
R ¹ ₃ SiX [2]
[In the formula [2], each R ¹ is independently of each other hydrogen or a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group in which a hydrogen element is substituted with a halogen element, and the formula [2] The total number of carbon atoms contained in R ¹ is 6 or more, X is a monovalent functional group in which the element bonded to the silicon element is nitrogen, and monovalent functional group in which the element bonded to the silicon element is oxygen Or a halogen group. ] 3. The wafer cleaning method according to claim 1, wherein the water repellent protective film forming agent is a silicon compound represented by the following general formula [3].
R ² (CH ₃ ) ₂ SiX [3]
[In the formula [3], R ² is an unsubstituted hydrocarbon group having 4 to 18 carbon atoms, or a hydrogen group in which a hydrogen element is substituted with a halogen element, and X is a monovalent element in which an element bonded to a silicon element is nitrogen A monovalent functional group in which the element bonded to the silicon element is oxygen, or a halogen group. ] The method for cleaning a wafer according to any one of claims 1 to 3, wherein the water repellent protective film forming agent is a silicon compound represented by the following general formula [4].
R ³ (CH ₃ ) ₂ SiX [4]
[In the formula [4], R ³ is a hydrocarbon group in which at least a part of hydrogen atoms having 4 to 18 carbon atoms is substituted with a fluorine element, and X is a monovalent element in which an element bonded to a silicon element is nitrogen A monovalent functional group in which the element bonded to the silicon element is oxygen, or a halogen group. ]

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