KR101593517B1 - Wafer washing method - Google Patents

Abstract

The present invention provides a cleaning method for improving a cleaning process that easily causes pattern collapse in a method of manufacturing a wafer having a concavo-convex pattern on its surface.
The present invention relates to a cleaning method of a wafer having a concavo-convex pattern on a surface, comprising: a step of cleaning the wafer with a cleaning liquid; a step of replacing the cleaning liquid held in the concave portion of the wafer with the water- Wherein the cleaning liquid contains 80 mass% or more of a solvent having a boiling point of 55 to 200 deg. C, and the temperature of the water-repellent chemical liquid provided in the replacing step is 40 deg. C or higher and less than the boiling point of the water- At least the surface of the concave portion is water-repellent.

Description

[0001] WAFER WASHING METHOD [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning technique of a substrate (wafer) in semiconductor device manufacturing and the like.

In semiconductor devices for networks and digital appliances, higher performance, higher performance, and lower power consumption are required. Therefore, the miniaturization of the circuit pattern is progressing, and the particle size causing the deterioration of the production yield is also made fine. As a result, a cleaning process for removing contaminants such as minute particles has been widely used. As a result, the cleaning process occupies 30 to 40% of the entire semiconductor manufacturing process.

On the other hand, cleaning of ammonia mixed cleaning agent, which has been conventionally carried out, is accompanied by a problem of damage to the wafer due to its basicity as the circuit pattern becomes finer. For this reason, replacement with a less corrosive hydrofluoric acid detergent has been progressing.

As a result, although the problem of damage to the wafer due to cleaning is improved, a problem caused by an increase in the aspect ratio of the pattern accompanying the miniaturization of the semiconductor device has surfaced. That is, after the cleaning or rinsing, a phenomenon that the pattern collapses when the gas-liquid interface passes through the pattern causes a significant decrease in the yield.

Patent Document 1 discloses a technique for suppressing pattern collapse by replacing the cleaning liquid with water with 2-propanol before the vapor-liquid interface passes through the pattern. However, it is known that there is a limit such that the aspect ratio of a pattern that can cope is 5 or less.

Patent Document 2 discloses a technique for suppressing pattern collapse by using a resist pattern as a target. This method suppresses pattern collapse by lowering the capillary force to an extreme limit. However, the disclosed technique is directed to a resist pattern, and the resist itself is modified. Since the resist can be finally removed together with the resist, there is no need to assume a method of removing the treating agent after drying, It is not applicable for this purpose.

As a method for preventing pattern collapse of a semiconductor device, use of a critical fluid, utilization of liquid nitrogen, and the like have been proposed. Patent Document 3 discloses a method of forming a cured photoresist, a residue after etching and / or a lower layer antireflection coating (BARC) on top of the same cured photoresist, post-etch residue and / or underlayer antireflection coating (BARC) A method of removing the cured photoresist, post-etch residue and / or BARC from a microelectronic device having sufficient time and sufficient contact to at least partially remove the photoresist, residue and / or BARC from the microelectronic device having the BARC thereon Contacting the microelectronic device with a dense fluid concentrate under conditions wherein the dense fluid concentrate comprises at least one co-solvent, optionally at least one oxidant / radical source, optionally at least one species And optionally at least one silicon-containing-layer deactivating agent, Chukmul components of this, (Ⅰ) or (Ⅱ):

(I) at least one fluoride source and optionally at least one acid, and

(II) at least one acid

≪ RTI ID = 0.0 > 1, < / RTI > However, a special cleaning device is required in comparison with the conventional cleaning process, and it is difficult to apply the cleaning device to a mass production process such as a poor throughput.

Patent Documents 4 and 5 disclose that the surface of a wafer on which a concave-convex pattern is formed by a film containing silicon is surface-modified by oxidation or the like and a water-soluble surfactant or a silane coupling agent is used on the surface to form a water- And the capillary force is reduced to prevent the pattern from falling down.

Patent Documents 6 and 7 disclose a process of treating a surface of a resin pattern provided on a substrate or a pattern of an etched pattern formed on a substrate by etching with a surface treatment solution containing a silylating agent and a solvent, And a step of cleaning the resin pattern or the pattern to be etched after the treatment.

Patent Document 8 discloses a method of manufacturing a semiconductor device, which comprises a step of forming a semiconductor device having a substrate and a dielectric layer having a structure protruding from the substrate, a step of cleaning the structure of the semiconductor device with an aqueous solution, And a hydrophobic treatment agent which reacts with the side wall of the protruded structure to form a hydrophobic layer on the side wall surface after the replacement, and a step of treating the structure with a second liquid containing a hydrophobic treatment agent .

Patent Document 9 discloses a cleaning agent for a silicon wafer having a fine concavo-convex pattern on its surface. The cleaning agent includes a cleaning liquid A and a cleaning liquid B. The cleaning liquid A is an aqueous solution, and the cleaning liquid B is a water- The cleaning liquid B is a mixture of a water-soluble compound containing a hydrophobic group and an alcoholic solution containing an alcoholic solvent, and a water or an acidic aqueous solution, wherein the cleaning liquid B is a hydrolyzable moiety causing a unit chemically bondable to the silicon element of the silicon wafer, The water repellent compound is mixed with the water repellent compound so that the total amount of the water repellent compound is in the range of from 0.2 to 20% by mass in the total amount of the cleaning liquid B, so that water is retained in the concave portion of the surface of the silicon wafer, Of silicon wafers is to be made 2.1 MN / m < 2 > It discloses a cleaning method of silicon wafer surface using a tablet.

Patent Document 10 discloses a cleaning agent for a silicon wafer having a fine concavo-convex pattern on its surface, wherein the cleaning agent for the silicon wafer includes at least an aqueous cleaning solution and a water-repellent cleaning solution for repellentizing at least concave portions of the concave-convex pattern during the cleaning process, Is composed of a water repellent compound containing a reactive moiety chemically bondable to a silicon element of a silicon wafer and a hydrophobic group, or 0.1% by mass or more of the water repellent compound and 100% by mass of the water repellent cleaning liquid are mixed with an organic solvent , The capillary force when assuming that water is retained in the concave portion of the surface of the silicon wafer that has been water-repellent by the water-repellent cleaning liquid is made to be 2.1 MN / m 2 or less, A surface cleaning method is disclosed.

Patent Document 11 discloses a cleaning agent for a silicon wafer having a fine concavo-convex pattern on its surface. The cleaning agent for the silicon wafer includes at least an aqueous cleaning solution and a water-repellent cleaning solution for repellentizing at least concave portions of the concave-convex pattern during the cleaning process, Is a mixture of a water repellent compound containing a reactive moiety chemically bondable to a silicon element of a silicon wafer and a hydrophobic compound containing a hydrophobic group and an organic solvent containing a nitrogen element-containing solvent, and the water repellent compound has a total amount of 100 parts by mass By mass, and the nitrogen element-containing solvent is mixed with nitrogen so that the element binding to nitrogen is carbon, water is contained in the concave portion of the surface of the silicon wafer which is water-repellent by the water-repellent cleaning liquid The capillary force was 2.1 MN / m < 2 > Of the surface of the silicon wafer using a cleaning agent for a silicon wafer.

Patent Document 12 discloses a cleaning agent for a silicon wafer having a fine concavo-convex pattern on its surface, wherein the cleaning agent for the silicon wafer includes at least an aqueous cleaning solution and a water-repellent cleaning solution for repellentizing at least concave portions of the concave-convex pattern during the cleaning process, Characterized in that a water repellent compound containing a reactive moiety capable of chemically bonding with the silicon element of the silicon wafer and a hydrophobic group containing a hydrophobic group and an organic solvent containing at least an alcohol solvent are mixed and contained, A cleaning method is disclosed.

As the wafer, a wafer having a silicon element on its surface has been generally used. However, wafers having elements such as titanium, tungsten, aluminum, copper, tin, tantalum, and ruthenium on the surface have been used . Patent Document 13 discloses a wafer in which a fine concavo-convex pattern is formed on a surface, at least a part of the concave portion of the concave-convex pattern is selected from the group consisting of titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, A water repellent protective film forming agent for forming a water repellent protective film on at least the surface of the concave portion at the time of cleaning of the wafer including at least one kind of substance which is easy to cause pattern collapse It is disclosed that the process can be improved.

Japanese Patent Application Laid-Open No. 2008-198958 Japanese Patent Application Laid-Open No. 5-299336 Japanese Patent Application Laid-Open No. 2008-547050 Japanese Patent Publication No. 4403202 Japanese Patent Application Laid-Open No. 2010-114467 Japanese Patent Application Laid-Open No. 2010-129932 International Publication No. 2010/047196 Pamphlet U.S. Published Patent Application No. 2010/0122711 International Publication No. 2010/074134 Pamphlet Japanese Patent Application Laid-Open No. 2010-192878 JP-A-2010-192879 Japanese Patent Application Laid-Open No. 2010-272852 Japanese Patent Publication No. 4743340

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning technique for a substrate (wafer) for the purpose of improving the production yield of a circuit patterned device having a fine and high aspect ratio in the production of semiconductor devices and the like, And a water repellent chemical solution for the purpose of improving the cleaning process that easily causes the uneven pattern collapse. Patent Documents 4 and 5 disclose that the reaction of the surface treatment agent is promoted by elevating the liquid temperature by performing an annealing treatment. However, in the case where the surface treatment agent is rapidly applied to the surface of the to- There is no consideration of promoting the reaction of the surface treatment agent to such an extent that a water repellent coating film can be sufficiently formed even in a state of being completely replaced There was room for improvement in shortening the time. Also in Patent Documents 6 to 13, there is room for improvement in shortening the time required for the surface treatment for the same reason. A water repellent coating is formed on at least a concave surface of a wafer to reduce the interaction between the liquid retained in the concave portion and the surface of the concave portion to prevent collapse of the concavity and convexity pattern. And it is an object of the present invention to provide a cleaning method capable of cleaning a wafer economically and more efficiently without damaging the throughput.

A cleaning method of a wafer of the present invention is a cleaning method of a wafer having a concavo-convex pattern on its surface,

A step of cleaning the wafer with a cleaning liquid,

A step of replacing the cleaning liquid held in the concave portion of the wafer with the water repellent chemical after cleaning,

And a step of drying the wafer,

The cleaning liquid contains 80% by mass or more of a solvent having a boiling point of 55 to 200 캜,

Characterized in that at least the surface of the concave portion is made water-repellent by making the temperature of the water-repellent chemical solution provided in the replacing step 40 DEG C or higher and lower than the boiling point of the water-repellent chemical solution. In this specification, the boiling point refers to a value at a pressure of 1 atm. The boiling point of the water-repellent chemical solution means the boiling point of the component having the largest amount in the mass ratio among the components contained in the water-repellent chemical solution.

The pattern collapse occurs when the vapor-liquid interface passes through the pattern during drying after cleaning the wafer with the cleaning liquid. This is caused by a difference in the height of the residual solution of the cleaning liquid between the portion where the aspect ratio of the pattern is large and the portion where the aspect ratio is large, thereby causing a difference in the capillary force acting on the pattern.

Therefore, if the capillary force is reduced, it is expected that the difference in the capillary force due to the difference in the height of the residual solution is reduced and the pattern collapse is solved. The magnitude of the capillary force is an absolute value of P obtained by the following equation, and it is expected that the capillary force can be reduced by decreasing? Or cos? From this equation.

P = 2 x? X cos? / S

(Where? Is the surface tension of the liquid held in the recess,? Is the contact angle between the surface of the recess and the liquid held in the recess, and S is the width of the recess).

The water-repellent chemical solution can reduce the surface energy of the part by forming a water-repellent coating on at least the concave surface of the concavo-convex pattern, and the water-repellent chemical solution interacts with water or other liquids (interface) For example, hydrogen bonding, intermolecular force, and the like. In particular, although the effect of reducing the interaction with water is great, it has an effect of reducing the interaction with liquids other than water and liquids other than water, and liquids other than water. This makes it possible to increase the contact angle of the liquid with respect to the article surface.

The water repellent film is formed on at least the concave surface of the concavo-convex pattern while the cleaning liquid is replaced with the water repellent chemical liquid and the chemical liquid is retained in at least the concave portion of the concavo-convex pattern. Therefore, when the liquid is removed from the concave portion, that is, when the liquid is dried, the water repellent film is formed on at least the concave portion surface of the concavo-convex pattern, so that the capillary force acting on the concave portion is small and pattern collapse is unlikely to occur Loses.

In order to form a water repellent coating on at least the concave surface of the concavo-convex pattern using the water repellent chemical solution in a short time, it is necessary to increase the film-forming ability of the chemical solution and to quickly replace the cleaning liquid held in the concavity with the water- It is valid.

When the temperature of the water-repellent chemical solution provided in the replacement step is 40 ° C or higher, the reaction or adsorption of the water-repellent chemical solution is promoted and the film-forming ability is enhanced, and as a result, the water-repellent film can be formed in a short time. Further, even if the state is completely undergoing the substitution, the water repellent film can be formed. However, if the temperature of the water-repellent liquid is made to be the boiling point of the liquid, the liquid becomes liable to evaporate quickly, and the surface of the wafer is liable to be dried, which is not preferable. Therefore, it is preferable that the water-repellent chemical has a temperature of 40 ° C or higher, lower than the boiling point of the water-repellent chemical, preferably 50 ° C or higher, (boiling point of the water-repellent chemical is -10 ° C) Lt; RTI ID = 0.0 > 10 C) < / RTI >

If the cleaning liquid contains 80% by mass or more of a solvent having a boiling point of 55 to 200 占 폚, the cleaning liquid is liable to evaporate when a water repellent liquid having a temperature of 40 占 폚 or more is supplied, Is easily replaced by a water-repellent chemical. As a result, a water repellent film is formed in a short time. Further, since the temperature of the supplied chemical liquid is 40 DEG C or higher and the temperature of the chemical liquid is lower than the boiling point, diffusion or convection is likely to occur between the cleaning liquid and the concave portion of the concavo-convex pattern, The cleaning liquid can be replaced with a water-repellent chemical in a short time. Therefore, it is particularly preferable that the cleaning liquid contains 80% by mass or more of a solvent having a boiling point of 60 to 180 캜, and more preferably 80% by mass or more of a solvent having a boiling point of 70 to 160 캜. If the cleaning liquid contains 80% by mass or more of a solvent having a boiling point of less than 55 캜, a chemical liquid at a temperature of 40 캜 or higher and lower than the boiling point of the water-repellent chemical liquid is supplied in the step of replacing the cleaning liquid with the water- There is a case where the cleaning liquid is suddenly boiled and the evaporation rate of the cleaning liquid is excessively high. As a result, there is a fear that the concavity and convexity pattern may be damaged due to the generation of bubbles or dust bubbles. If the cleaning liquid contains 80% by mass or more of a solvent having a boiling point of more than 200 ° C, it is preferable that the cleaning liquid is supplied at a temperature of 40 ° C or higher and lower than the boiling point of the water- The evaporation of the cleaning liquid is slow, so that a long time is required for the replacement. As a result, a long time is also required to develop water repellency on the surface of the wafer. It is more preferable that the above-mentioned cleaning liquid is a solvent having a boiling point of 55 to 200 캜, since it is easy to manage the temperature of the water-repellent chemical liquid for avoiding abrupt evaporation of the cleaning liquid, generation of bubbles,

It is preferable that the cleaning liquid is at least one liquid selected from the group consisting of an organic solvent, water, and an aqueous solution in which at least one of an organic solvent, an acid, an alkali, and an oxidizer is mixed with water. An aqueous solution in which at least one of water, water, and an organic solvent, an acid, an alkali, and an oxidizing agent is mixed is hereinafter sometimes referred to as an aqueous liquid.

The water-repellent chemical liquid is used by replacing the cleaning liquid with the chemical liquid in the cleaning process of the wafer on which the concavo-convex pattern is formed. Further, the substituted water repellent liquid may be replaced with another cleaning liquid.

The water repellent coating film may or may not necessarily be formed continuously, but it is more preferable that the water repellent film film is formed continuously and uniformly, since it can impart water repellency to the film.

The wafer is a wafer (hereinafter sometimes referred to as a " silicon wafer ") containing a silicon element on the surface of the concave portion of the concavo-convex pattern, and the water repellent chemical solution is a silicon compound A represented by the following general formula [ , Or a compound containing silicon compound A and an acid or base. The method of cleaning the silicon wafer using the water-repellent chemical solution for silicon wafer is described as the first aspect of the present invention (hereinafter sometimes referred to as " first method "). Further, the chemical solution may be described as " water-repellent chemical solution for silicon wafer ".

(R ¹ ) _a Si (H) _b X ¹ _{4 -ab} [1]

[In the formula [1], R ¹ is a monovalent organic group including monovalent hydrocarbon groups of 1 to 18 carbon atoms, in which some or all of hydrogen atoms may be substituted with fluorine atoms. X ¹ represents a monovalent functional group in which the element bonding to the silicon element is nitrogen, a monovalent functional group in which the element bonding to the silicon element is oxygen, a halogen group, a nitrile group, and -CO-NH-Si ( CH ₃ ) ₃ . a is an integer of 1 to 3, b is an integer of 0 to 2, and the sum of a and b is 1 to 3.]

The water-repellent chemical solution contains an acid, and the acid is selected from the group consisting of hydrogen chloride, sulfuric acid, perchloric acid, phosphoric acid, a sulfonic acid and its anhydride represented by the following general formula [2], a carboxylic acid represented by the following general formula [3] At least one member selected from the group consisting of an alkyl borate ester, an aryl borate ester, tris (trifluoroacetoxy) boron, trialkoxyboroxine, trifluoroboron, and a silicon compound B represented by the following general formula [4] .

R ² S (O) ₂ OH [2]

[In the formula [2], R ² is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms.]

R ³ COOH [3]

[In the formula [3], R ³ is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with a fluorine atom.]

(R ⁴ ) _c Si (H) _d X ² _{4 -cd} [4]

[In the formula [4], R ⁴ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be substituted with fluorine atoms in part or all of hydrogen atoms. X ² is, independently of each other, a chloro group, -OCO-R ⁵ (R ⁵ is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms), and -OS (O) _2- R ⁶ (R ⁶ represents at least one group selected from the group consisting of a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms). c is an integer of 1 to 3, d is an integer of 0 to 2, and the sum of c and d is 1 to 3.]

Further, the acid is preferably the silicon compound B represented by the above general formula [4], and is preferably selected from the group consisting of trimethylsilyl trifluoroacetate, trimethylsilyltrifluoromethanesulfonate, dimethylsilyltrifluoroacetate, dimethylsilyltrifluoromethane Butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl Is selected from the group consisting of trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, decyldimethylsilyltrifluoromethanesulfonate, dodecyldimethylsilyl trifluoroacetate, and dodecyldimethylsilyltrifluoromethanesulfonate Preferably, at least one .

The water-repellent chemical solution contains a base and the base is selected from the group consisting of ammonia, N, N, N ', N'-tetramethylethylenediamine, triethylenediamine, dimethylaniline, alkylamine, dialkylamine, trialkylamine, , Piperazine, N-alkyl morpholine, and silicon compound C represented by the following general formula [5].

(R ⁷ ) _e Si (H) _f X ³ _{4 -ef} [5]

[In the formula [5], R < ⁷ > is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms. X ³ is a monovalent functional group that is independent of each other and an element which bonds with the silicon element is nitrogen and may contain a fluorine atom or a silicon element. e is an integer of 1 to 3, f is an integer of 0 to 2, and the sum of e and f is 1 to 3.]

The water repellent film formed using the water repellent chemical solution for silicon wafer reacts with a silanol group in which X ^{1 in} the general formula [1] is a reaction site on the silicon wafer surface, and the silicon compound A reacts with silicon- And is chemically bonded to the silicon element. R ¹ in the general formula [1] reduces the surface energy of the concave portion to reduce interaction between water and other liquids and the surface of the water-repellent coating film (interface), for example, hydrogen bonding, intermolecular force, etc. , The contact angle of the liquid with respect to the article surface can be increased.

The acid or base, which may be contained in the chemical solution, is said to promote the reaction between the silicon compound A and the silicon element of the silicon-based wafer. When the acid or base is present in the water-repellent chemical solution for the silicon-based wafer, the water-repellent film can be formed in a short time. The rate at which the water-repellent film is formed on the silicon-based wafer surface, that is, the rate at which the silicon-based wafer surface exhibits water repellency, is determined by the rate at which the component derived from the silicon compound A bonds to the reaction site on the surface of the silicon- I will lose. When the above-mentioned acid or base is present, the component derived from the silicon compound A can quickly react with the silanol group which is the reaction site of the surface of the concavo-convex pattern of the silicon wafer. Therefore, Can be given. The acid or base may form part of the water-repellent coating.

The silicon compound A may be at least one selected from the group consisting of hexamethyldisilazane, trimethylsilyldimethylamine, trimethylsilyldiethylamine, tetramethyldisilazane, dimethylsilyldimethylamine, dimethylsilyldiethylamine, 1,3-dibutyltetramethyldi But are not limited to, silazane, butyldimethylsilyldimethylamine, butyldimethylsilyldiethylamine, 1,3-dihexyltetramethyldisilazane, hexyldimethylsilyldimethylamine, hexyldimethylsilyldiethylamine, 1,3-dioctyltetramethyldi But are not limited to, silazane, octyldimethylsilyldimethylamine, octyldimethylsilyldiethylamine, 1,3-didecyltetramethyldisilazane, decyldimethylsilyldimethylamine, decyldimethylsilyldiethylamine, 1,3-didodecyltetramethyldi It is preferably at least one selected from the group consisting of silazane, dodecyldimethylsilyldimethylamine and dodecyldimethylsilyldiethylamine.

The wafer may further include at least one element selected from the group consisting of titanium, tungsten, aluminum, copper, tin, tantalum and ruthenium on the surface of the concave portion of the concavo-convex pattern (Hereinafter sometimes referred to as a " metal-based wafer "), wherein the water-repellent chemical is at least one selected from the group consisting of compounds represented by the following general formulas [6] to [12] And a solvent. Further, the chemical solution may be described as " water-repellent chemical solution for metal-based wafer ". A method for cleaning a metal-based wafer using the water-repellent chemical solution for a metal-based wafer is described as a second aspect of the present invention (hereinafter, sometimes referred to as a "second method").

R ⁸ -P (= O) - (OH) _g (R ⁹ ) _2-g [6]

[In the formula [6], R ⁸ is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with a fluorine atom. R ⁹ are each independently a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with a fluorine atom. and g is an integer of 0 to 2.]

R ¹⁰ -C (═O) -X ⁴ [7]

[In the formula [7], R ¹⁰ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. X ⁴ represents a group selected from the group consisting of a fluoro group, a chloro group, a bromo group, and an iodo group.

R ¹¹ R ¹² R ¹³ N [8]

[Wherein R ¹¹ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. R ¹² is a monovalent organic group containing a hydrogen atom, a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. R ¹³ is a monovalent organic group containing a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms.

R ^{14 is} -C (= O) -X ⁵ -X ⁶ [9]

Of the formula [9], R ¹⁴ is a monovalent organic group having a carbon number of which comprises a monovalent organic group in the alkyl chain, or fluoro carbon number of from 1 to 8 comprising a hydrocarbon of from 1 to 18. X ⁵ represents an oxygen element or a sulfur element and X ⁶ represents a hydrogen atom, an alkyl group, an aromatic group, a pyridyl group, a quinolyl group, a succinimide group, a maleimide group, a benzoxazole group, a benzothiazole group, And the hydrogen atom in these groups may be substituted with an organic group.

R ¹⁵ (X ⁷ ) _h [10]

X ⁷ is at least one group selected from the group consisting of a cyclic structure including an isocyanate group, a mercapto group, an aldehyde group, a -CONHOH group and a nitrogen atom, and h is at least one group selected from the group consisting of R ¹⁵ is an organic group containing a hydrocarbon group having 1 to 18 carbon atoms or an organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms, and the above-mentioned h isocyanate group, mercapto group , A cyclic structure including an aldehyde group, a -CONHOH group, and a nitrogen element, is substituted with the same number of hydrogen atoms.

R ¹⁶ -X ⁸ [11]

Wherein X ⁸ is a cyclic structure containing a sulfur element and R ¹⁶ is a monovalent organic group containing a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a fluoroalkyl group having 1 to 8 carbon atoms Is a monovalent organic group containing a chain.]

R ^{17 is} -C (= O) -X ⁹ -C (= O) -R ¹⁸ [12]

[In the formula [12], R ¹⁷ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. R ¹⁸ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. X ⁹ represents an oxygen element or a sulfur element.]

The water repellent film formed by using the water repellent chemical solution for the metal-based wafer can be obtained by using a compound selected from the compounds represented by the general formulas [6] to [12] and salt compounds thereof, . In addition, the formation of the water-repellent coating is carried out by adsorbing on the surface of a substance containing a functional metal element having affinity for a substance containing a metal-based element and / or by reacting the functional substance with the surface of the substance, So that the adsorbent is adsorbed. The functional group is a group represented by -C (= O) -X ⁴ in the general formula [7], a group represented by a P-OH group and / or a P═O group in the general formula [ (8) is an N element and is a group represented by -C (= O) -X ⁵ -X ⁶ in the general formula [9], a group represented by (X ⁷ ) _h in the general formula [10] Is a group represented by -X ⁸ in the formula [11], and a group represented by -C (= O) -X ⁹ -C (= O) - in the formula [12]. Here, having affinity means that van der Waals force or electrostatic interaction acts between the surface of the substance including the metal element and the functional part of the compound. Further, in the general formula [6] R ^8, represented by the general formula [7] of the R ^10, the general formula [8] of the R ^11, the general formula [9] of the R ^14, the general formula [10] R ^15, formula when [11] R ^16, and the general formula [12] R ¹⁷ and R ¹⁸ of the is the fractional part of the compound, is the compounds have been adsorbed on the metallic element of the metal-based wafer, the art towards the outside from the art metal-based wafer surface prime number And as a result, the surface energy of the concave portion is reduced to have an effect of reducing interaction (for example, hydrogen bonding, intermolecular force, etc.) between water and other liquids and the surface of the water-repellent coating film (interface). This makes it possible to increase the contact angle of the liquid with respect to the article surface.

Further, the present invention is a water-repellent chemical used in the cleaning method of a wafer described in any one of the above-mentioned items.

In the present specification, when both silicon-based wafers and metal-based wafers are referred to, they may be simply referred to as " wafers ". When both the water-repellent chemical solution for a silicon-based wafer and the water-repellent chemical solution for a metal-based wafer are referred to, they may be simply described as " water-repellent chemical solution ".

The cleaning method of the present invention is a cleaning method for forming a water repellent film on the concave surface of a wafer and reducing the interaction between the liquid held in the concave portion and the surface of the concave portion, It can be formed in a short time. Therefore, the method of producing a wafer having a concavo-convex pattern on the surface, which is performed using the water-repellent chemical solution of the present invention, has high productivity.

1 is a schematic plan view showing an example of a wafer 1 whose surface is a surface having a concavo-convex pattern 2. Fig.
Fig. 2 shows a part of a cross section taken along the line a-a 'in Fig.
3 is a schematic view showing a state in which the concave portion 4 holds the cleaning liquid 8 in the cleaning process.
4 is a schematic diagram showing a state in which a water-repellent chemical 9 is provided on a wafer in which a cleaning liquid 8 is held in a recess 4 in a cleaning process.
5 shows a schematic diagram of a state in which the water repellent coating film 12 is formed by holding the water repellent chemical 9 in the recess 4 in the replacement step.

The present invention relates to a cleaning method of a wafer having a concavo-convex pattern on a surface, comprising: a step of cleaning the wafer with a cleaning liquid; a step of replacing the cleaning liquid held in the concave portion of the wafer with the water- Wherein the cleaning liquid contains 80 mass% or more of a solvent having a boiling point of 55 to 200 deg. C, and the temperature of the water-repellent chemical liquid provided in the replacing step is 40 deg. C or higher and less than the boiling point of the water- And at least the surface of the concave portion is water-repellent.

When the wafer having the concavo-convex pattern on the surface is washed with various liquids and the liquid is removed by drying or the like, when the width of the concavity is small and the aspect ratio of the convex portion is large, pattern collapse is apt to occur. The concavo-convex pattern is defined as shown in Figs. Fig. 1 shows a schematic plan view of an example of a wafer 1 having a surface having a concavo-convex pattern 2, and Fig. 2 shows a part of a cross section taken along the line a-a 'in Fig. The width 5 of the concave portion is represented by the distance between the convex portion 3 and the convex portion 3 as shown in Fig. 2 and the aspect ratio of the convex portion is the width 6 of the convex portion as the width 7 of the convex portion Respectively. Pattern collapse in the cleaning process is likely to occur when the width of the recess is 70 nm or less, particularly 45 nm or less, and when the aspect ratio is 4 or more, particularly 6 or more.

In the cleaning method of the present invention, a cleaning liquid containing at least 80 mass% of a solvent having a boiling point of 55 to 200 deg. C is held in at least a concave portion of the concavo-convex pattern, and the cleaning liquid is held in at least concave portions of the concavo- The washing liquid is replaced with the water-repellent chemical liquid.

3 is a schematic view showing a state in which the concave portion 4 holds the cleaning liquid 8 in the cleaning process. The wafer in the schematic view of Fig. 3 shows a part of a cross section along the line a-a 'in Fig. A water repellent chemical solution is provided on the wafer in which the cleaning liquid 8 is held in the concave portion 4 in the cleaning process.

Fig. 4 is a schematic diagram showing a state in which the water repellent liquid medicine 9 is provided on the wafer with the recess 4 retaining the cleaning liquid 8. Fig. At this time, the concave portion is replaced with the water-repellent chemical 9 from the cleaning liquid 8, but the cleaning liquid 8 contains 80% by mass or more of a solvent having a boiling point of 55 to 200 캜, , The temperature is raised to 40 ° C or higher and less than the boiling point of the water-repellent chemical liquid. Therefore, mixing of the cleaning liquid and the water-repellent chemical liquid tends to proceed by diffusion or convection as indicated by 10 in the drawing, The evaporation of the cleaning liquid such as the bar becomes easy to proceed, and as a result, the replacement progresses in a short time.

5 shows a schematic diagram of a state in which the water repellent coating film 12 is formed by holding the water repellent chemical 9 in the recess 4 in the replacement step. The water repellent coating 12 is formed on the surface of the concave portion 4, so that the surface is water-repellent.

Hereinafter, the first method will be described. The water-repellent chemical solution for silicon-based wafers preferably contains the silicon compound A represented by the general formula [1], or contains the silicon compound A and an acid or base.

The monovalent functional group having an element bonded to the silicon element, which is an example of X ^{1 in} the above general formula [1], may be nitrogen as well as elements such as silicon, sulfur and halogen as well as hydrogen, carbon, nitrogen and oxygen. Examples of the functional group include an isocyanate group, an amino group, a dialkylamino group, an isothiocyanate group, an azide group, an acetamide group, -N (CH ₃ ) C (O) CH ₃ , -N (CH ₃ ) _{CF 3, -N = C (CH} 3) OSi (CH 3) 3, -N = C (CF 3) OSi (CH 3) 3, -NHC (O) -OSi (CH 3) 3, -NHC (O _{) -NH-Si (CH 3)} 3, an imidazole ring (formula [13]), the oxazolidinone ring (the following formula [15]), morpholine ring (the following formula [14]), -NH-C ( O) -Si (CH ₃ ) ₃ , -N (H) _2-i (Si (H) _j R ¹⁹ _3-j ) _{i wherein} R ¹⁹ is a group in which some or all hydrogen atoms may be substituted with fluorine atoms A monovalent hydrocarbon group having 1 to 18 carbon atoms, i is 1 or 2, and j is an integer of 0 to 2).

The monovalent functional group in which the element bonding to the silicon element, which is an example of X ¹ in the general formula [1], is oxygen may contain not only hydrogen, carbon, nitrogen and oxygen but also elements such as silicon, sulfur and halogen . Alkoxy group, examples of such an organic _{group, -OC (CH 3) = CHCOCH} 3, -OC (CH 3) = N-Si (CH 3) 3, -OC (CF 3) = N-Si (CH 3) 3, -O-CO-R ²⁰ (R ²⁰ is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with a fluorine element or the like), and even if some or all of hydrogen elements are substituted with fluorine elements or the like And an alkylsulfonate group.

The halogen group which is an example of X ¹ in the general formula [1] includes a chloro group, a bromo group, and an iodo group.

R ¹ in the general formula [1] reduces the surface energy of the water-repellent coating, and the interaction between water and other liquids and the surface of the water-repellent coating (interface), for example, hydrogen bonding, . In particular, although the effect of reducing the interaction with water is great, it has an effect of reducing the interaction with liquids other than water and liquids other than water, and liquids other than water. This makes it possible to increase the contact angle of the liquid with respect to the article surface.

As the silicon compound A represented by the general formula (1), for example, _{CH 3 Si (OCH 3) 3} , C 2 H 5 Si (OCH 3) 3, C 3 H 7 Si (OCH 3) 3, C 4 _{H 9 Si (OCH 3) 3} , C 5 H 11 Si (OCH 3) 3, C 6 H 13 Si (OCH 3) 3, C 7 H 15 Si (OCH 3) 3, C 8 H 17 Si (OCH 3 _{) 3, C 9 H 19 Si} (OCH 3) 3, C 10 H 21 Si (OCH 3) 3, 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 , (CH ₃ ) ₂ Si (OCH ₃ ) ₂ , C ₂ H ₅ Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₂ H ₅ ) ₂ Si _{3) 2, C 3 H 7} Si (CH 3) (OCH 3) 2, (C 3 H 7) 2 Si (OCH 3) 2, C 4 H 9 Si (CH 3) (OCH 3) 2, (C _{4 H 9) 2 Si (OCH} 3) 2, C 5 H 11 Si (CH 3) (OCH 3) 2, C 6 H 13 Si (CH 3) (OCH 3) 2, C 7 H 15 Si (CH 3 _{) (OCH 3) 2, C} 8 H 17 Si (CH 3) (OCH 3) 2, C 9 H 19 Si (CH 3) (OCH 3) 2, C 10 H 21 Si (CH 3) (OCH 3) _{2, C 11 H 23 Si (} CH 3) (OCH 3) 2, C 12 H 25 Si (CH 3) (OCH 3) 2, C 13 H 27 Si (CH 3) (OCH 3) 2 _{, C 14 H 29 Si (CH} 3) (OCH 3) 2, C 15 H 31 Si (CH 3) (OCH 3) 2, C 16 H 33 Si (CH 3) (OCH 3) 2, C 17 H 35 _{Si (CH 3) (OCH 3} ) 2, C 18 H 37 Si (CH 3) (OCH 3) 2, (CH 3) 3 SiOCH 3, C 2 H 5 Si (CH 3) 2 OCH 3, (C 2 _{H 5) 2 Si (CH 3} ) OCH 3, (C 2 H 5) 3 SiOCH 3, C 3 H 7 Si (CH 3) 2 OCH 3, (C 3 H 7) 2 Si (CH 3) OCH 3, _{(C 3 H 7) 3 SiOCH} 3, C 4 H 9 Si (CH 3) 2 OCH 3, (C 4 H 9) 3 SiOCH 3, C 5 H 11 Si (CH 3) 2 OCH 3, C 6 H 13 _{Si (CH 3) 2 OCH 3} , C 7 H 15 Si (CH 3) 2 OCH 3, C 8 H 17 Si (CH 3) 2 OCH 3, C 9 H 19 Si (CH 3) 2 OCH 3, C 10 _{H 21 Si (CH 3) 2} OCH 3, C 11 H 23 Si (CH 3) 2 OCH 3, C 12 H 25 Si (CH 3) 2 OCH 3, C 13 H 27 Si (CH 3) 2 OCH 3, _{C 14 H 29 Si (CH 3} ) 2 OCH 3, C 15 H 31 Si (CH 3) 2 OCH 3, C 16 H 33 Si (CH 3) 2 OCH 3, C 17 H 35 Si (CH 3) 2 OCH _{3, C 18 H 37 Si (} CH 3) 2 OCH 3, (CH 3) 2 Si (H) OCH 3, CH 3 Si (H) 2 OCH 3, (C 2 H 5) 2 Si (H) OCH 3 _{, C 2 H 5 Si (H} ) 2 OCH 3, C 2 H 5 Si (CH 3) (H) OCH 3, (C 3 H 7) 2 Si (H) OCH 3 , such as an alkyl silane, or CF of ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₂ F ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , C ₃ F ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ and C ₄ F ₉ CH ₂ CH ₂ Si _{OCH 3) 3, C 5 F} 11 CH 2 CH 2 Si (OCH 3) 3, C 6 F 13 CH 2 CH 2 Si (OCH 3) 3, C 7 F 15 CH 2 CH 2 Si (OCH 3) 3, _{C 8 F 17 CH 2 CH 2} Si (OCH 3) 3, CF 3 CH 2 CH 2 Si (CH 3) (OCH 3) 2, C 2 F 5 CH 2 CH 2 Si (CH 3) (OCH 3) 2 , C ₃ F ₇ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , C ₄ F ₉ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si _{3) (OCH 3) 2,} C 6 F 13 CH 2 CH 2 Si (CH 3) (OCH 3) 2, C 7 F 15 CH 2 CH 2 Si (CH 3) (OCH 3) 2, C 8 F 17 _{CH 2 CH 2 Si (CH 3} ) (OCH 3) 2, CF 3 CH 2 CH 2 Si (CH 3) 2 OCH 3, C 2 F 5 CH 2 CH 2 Si (CH 3) 2 OCH 3, C 3 F _{7 CH 2 CH 2 Si (CH} 3) 2 OCH 3, C 4 F 9 CH 2 CH 2 Si (CH 3) 2 OCH 3, C 5 F 11 CH 2 CH 2 Si (CH 3) 2 OCH 3, C 6 _{F 13 CH 2 CH 2 Si (} CH 3) 2 OCH 3, C 7 F 15 CH 2 CH 2 Si (CH 3) 2 OCH 3, C 8 F 17 CH 2 CH 2 Si (CH 3) 2 OCH 3, CF _{3 CH 2 CH 2 Si (CH} 3) (H) OCH 3 , such as fluoro alkyl silane, wherein the alkyl or methoxy silane or A methyl group portion of a methoxy group of an alkyl silane to the fluoro, the alkoxysilane compound which is substituted with a monovalent hydrocarbon group of 2 to 18 carbon atoms, or the methoxy _{group, -OC (CH 3) = CHCOCH} 3, -OC ( CH ₃ ) = N-Si (CH ₃ ) ₃ , -OC (CF ₃ ) = N-Si (CH ₃ ) ₃ , -O-CO-R ²⁰ (R ²⁰ is a hydrogen atom, A monovalent hydrocarbon group having 1 to 18 carbon atoms which may be substituted), an alkylsulfonate group, an isocyanate group, an amino group, a dialkylamino group, an isothiocyanate group, an isocyanate group, an azide group, an acetamide _{group, -N (CH 3) C (} O) CH 3, -N (CH 3) C (O) CF 3, -N = C (CH 3) OSi (CH 3) 3, - _{N = C (CF 3) OSi} (CH 3) 3, -NHC (O) -OSi (CH 3) 3, -NHC (O) -NH-Si (CH 3) 3, an imidazole ring, oxazolidinone ring , morpholine ring, -NH-C (O) -Si (CH 3) 3, -N (H) 2-i (Si (H) j R 19 3-j) i (R 19 is a part of or all of the hydrogen source I is 1 or 2, and j is an integer of 0 to 2), a chloro group, a bromo group, an iodo group, a nitrile group, or a -CO- NH-Si (CH ₃ ) ₃ , and the like.

When the number of X ^{1 in} the silicon compound A represented by 4-ab in the general formula [1] is 1, it is more preferable because the water repellent coating can be formed homogeneously.

R ¹ in the above general formula [1] is at least one group selected from a monovalent hydrocarbon group having 1 to 18 carbon atoms, in which some or all hydrogen atoms may be substituted with fluorine atoms, Is at least one group selected from C _m H _{2m +1} (m = 1 to 18) and C _n F _{2n + 1} CH ₂ CH ₂ (n = 1 to 8), water repellency The wettability of the surface can be further lowered when the film is formed, that is, the water repellency can be imparted to the surface. When m is 1 to 12 and n is 1 to 8, the water repellent film can be formed on the surface of the concavo-convex pattern in a short time.

Among them, the silicon compound A is preferably at least one member selected from the group consisting of hexamethyldisilazane, trimethylsilyldimethylamine, trimethylsilyldiethylamine, tetramethyldisilazane, dimethylsilyldimethylamine, dimethylsilyldiethylamine, 1,3-dibutyltetramethyl Butyldimethylsilyldimethylamine, butyldimethylsilyldiethylamine, 1,3-dihexyltetramethyldisilazane, hexyldimethylsilyldimethylamine, hexyldimethylsilyldiethylamine, 1,3-dioctyltetramethyl Dimethylsilyldimethylamine, octyldimethylsilyldiethylamine, 1,3-didecyltetramethyldisilazane, decyldimethylsilyldimethylamine, decyldimethylsilyldiethylamine, 1,3-didodecyltetramethyl Particularly preferred are disilazane, dodecyldimethylsilyldimethylamine and dodecyldimethylsilyldiethylamine.

The acid may be at least one selected from the group consisting of hydrogen chloride, sulfuric acid, perchloric acid, phosphoric acid, the sulfonic acid and its anhydride represented by the general formula [2], the carboxylic acid and its anhydride represented by the general formula [3], the alkyl borate ester, It is preferably at least one selected from the group consisting of tris (trifluoroacetoxy) boron, trialkoxyboroxine, trifluoroboron, and silicon compound B represented by the above general formula [4].

Examples of the sulfonic acid and its anhydride represented by the above general formula [2] include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride. Examples of the carboxylic acid and its anhydride include acetic acid, trifluoroacetic acid, pentafluoropropionic acid, acetic anhydride, trifluoroacetic anhydride, pentafluoropropionic anhydride and the like. As the silicon compound B represented by the general formula [4] Silane, alkylsilylalkyl sulfonate and alkylsilyl ester are preferable, and trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl Trifluoroacetate, butyldimethylsilyltrifluoromethane < RTI ID = 0.0 > Hexyldimethylsilyl trifluoroacetate, decyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyltrifluoroacetate, decyldimethylsilyl Trifluoromethanesulfonate, dodecyldimethylsilyl trifluoroacetate, dodecyldimethylsilyltrifluoromethanesulfonate, and the like.

In addition, the base may be selected from the group consisting of ammonia, N, N ', N'-tetramethylethylenediamine, triethylenediamine, dimethylaniline, alkylamine, dialkylamine, trialkylamine, pyridine, , And the silicon compound C represented by the above general formula [5].

The reaction between the silicon compound A and the silanol group as the reaction site on the surface of the silicon wafer is promoted by the acid or base which may be contained in the chemical liquid. Therefore, the surface of the silicon wafer Excellent water repellency can be imparted. The acid or base may form part of the water-repellent coating.

In consideration of the reaction promoting effect, it is preferable that the above-mentioned chemical liquid contains an acid. Particularly, it is preferable to use an acid such as hydrogen chloride, Bronsted acid of strong acid such as sulfuric acid or perchloric acid, trifluoromethanesulfonic acid or trifluoromethanesulfonic acid Or a carboxylic acid in which some or all of the hydrogen atoms of the alkanesulfonic acid or its acid anhydride in which all the hydrogen elements are substituted with fluorine atoms, trifluoroacetic acid, trifluoroacetic anhydride or pentafluoropropionic acid, Acid anhydrides, chlorosilanes, alkylsilylalkyl sulfonates in which some or all hydrogen elements are substituted with fluorine atoms, and alkylsilyl esters in which some or all hydrogen elements are substituted with fluorine atoms are particularly preferable. The alkylsilyl ester is obtained by bonding an alkyl group and -O-CO-R 'group (R' is an alkyl group) to a silicon element. The acid included in the chemical liquid may be generated by the reaction. For example, an alkylchlorosilane and an alcohol may be reacted to form the resulting alkylalkoxysilane as a silicon compound A, the resulting hydrochloric acid may be used as an acid, A water-repellent chemical solution containing an alcohol that has not been consumed as a solvent may be obtained.

Further, the acid is preferably the silicon compound B represented by the above general formula [4], and is preferably selected from the group consisting of trimethylsilyl trifluoroacetate, trimethylsilyltrifluoromethanesulfonate, dimethylsilyltrifluoroacetate, dimethylsilyltrifluoromethane Butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl Is selected from the group consisting of trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, decyldimethylsilyltrifluoromethanesulfonate, dodecyldimethylsilyl trifluoroacetate, and dodecyldimethylsilyltrifluoromethanesulfonate Preferably, at least one .

The silicon compound B represented by the above general formula [4] may be obtained by a reaction. For example, it is possible to use at least one silicon compound D represented by the following general formula [16] and at least one selected from the group consisting of trifluoroacetic acid, trifluoroacetic acid anhydride, trifluoromethanesulfonic acid and trifluoromethanesulfonic acid anhydride Quot; acid D " in some cases).

(R ²¹ ) _p (H) _q SiX ¹⁰ _{4 -pq} [16]

(Wherein R ²¹ is each independently selected from C _m H _{2m +1} (m = 1 to 18), and C _n F _{2n + 1} CH ₂ CH ₂ (n = 1 to 8) P is an integer of 1 to 3, q is an integer of 0 to 2, and the sum of p and q is 1 to 3. X ¹⁰ is independently from each other, and the element bonding with the silicon element is nitrogen 1 represents a divalent functional _{^{group. (R 21) p (H}} ) q Si- Examples of _{(CH 3) 3 Si-, (} CH 3) 2 (H) Si-, (C 4 H 9) (CH 3) 2 Si _{-, (C 6 H 13)} (CH 3) 2 Si-, (C 8 H 17) (CH 3) 2 Si-, and _{(C 10 H 21) (CH} 3) 2 Si-, (C 12 H 25 ) (CH ₃ ) ₂ Si-, and the like.

For example, when hexamethyldisilazane as the silicon compound D and trifluoroacetic acid anhydride as the acid D are mixed, anhydrous trifluoroacetic acid reacts on the spot to obtain trimethylsilyl trifluoroacetate as the silicon compound B Loses.

For example, when hexamethyldisilazane is mixed as the silicon compound D and trifluoromethanesulfonic acid is added as the acid D, trifluoromethanesulfonic anhydride reacts on-the-fly to form trimethylsilyltrifluoro Methanesulfonate is obtained.

For example, when tetramethyldisilazane as the silicon compound D and trifluoroacetic acid as the acid D are mixed, anhydrous trifluoroacetic acid reacts on-the-fly, and dimethylsilyltrifluoroacetate as the silicon compound B is reacted .

For example, when tetramethyldisilazane as the silicon compound D and trifluoromethanesulfonic acid as the acid D are mixed, trifluoromethanesulfonic anhydride reacts on the spot to give dimethylsilyltrifluoro Methanesulfonate is obtained.

Further, for example, when 1,3-dibutyltetramethyldisilazane is mixed as the silicon compound D and trifluoroacetic acid is added as the acid D, trifluoroacetic anhydride reacts on-the-fly to obtain butyl Dimethylsilyltrifluoroacetate is obtained.

In addition, for example, when 1,3-dibutyltetramethyldisilazane is mixed as the silicon compound D and trifluoromethanesulfonic acid is added as the acid D, trifluoromethanesulfonic anhydride reacts on the spot to form the silicon compound B Butyldimethylsilyltrifluoromethanesulfonate is obtained.

In addition, for example, when 1,3-dioctyltetramethyldisilazane is mixed as the silicon compound D and trifluoroacetic acid is added as the acid D, trifluoroacetic anhydride reacts on-the-spot to form octyl Dimethylsilyltrifluoroacetate is obtained.

When, for example, 1,3-dioctyltetramethyldisilazane as the silicon compound D and trifluoromethanesulfonic acid as the acid D are mixed, anhydrous trifluoromethanesulfonic acid reacts on the spot to form the silicon compound B Octyldimethylsilyltrifluoromethanesulfonate is obtained.

In addition, for example, when 1,3-dimethyidetetramethyldisilazane is mixed as the silicon compound D and trifluoroacetic acid is added as the acid D, trifluoroacetic anhydride reacts on-the-fly, Dimethylsilyltrifluoroacetate is obtained.

In addition, for example, when 1,3-dimethyidetetramethyldisilazane is mixed as the silicon compound D and trifluoromethanesulfonic acid is used as the acid D, anhydrous trifluoromethanesulfonic acid is reacted on the spot to form the silicon compound B Decyldimethylsilyltrifluoromethanesulfonate is obtained.

When, for example, octyldimethylsilyldimethylamine as the silicon compound D and trifluoroacetic acid anhydride as the acid D are mixed, anhydrous trifluoroacetic acid reacts on-the-spot to form octyldimethylsilyl trifluoroacetate Is obtained.

For example, when desilyldimethylsilyldimethylamine as the silicon compound D and anhydrous trifluoroacetic acid as the acid D are mixed, anhydrous trifluoroacetic acid reacts on-the-spot to give decyldimethylsilyltrifluoroacetate Is obtained.

Also, a water-repellent chemical solution for a silicon-based wafer prepared by reacting the acid D with at least one member selected from anhydrous trifluoroacetic acid and anhydrous trifluoromethane sulfonic acid to obtain the silicon compound B, or The water repellent chemical solution for silicon wafers prepared using the silicon compound A and the silicon compound B as a starting material is more preferable because of its excellent stability.

The water repellent chemical solution for a silicon wafer of the present invention is characterized in that the silicon compound D is excessively added to the acid D and the excess of the silicon compound D not consumed in the reaction contributes to the formation of the water repellent film as the silicon compound A It is acceptable. The number of moles of the silicon compound D is preferably 0.2 to 100,000 times, more preferably 0.5 to 50,000 times, and further preferably 1 to 10000 times the number of moles of the acid D.

If the silicon compound B represented by the general formula [4] is obtained, a reaction other than the reaction of the silicon compound D and the acid D may be used.

The monovalent functional group represented by X ¹⁰ in the above general formula [16] wherein the element bonding to the silicon element is nitrogen may contain not only hydrogen, carbon, nitrogen, oxygen, but also elements such as silicon, sulfur and halogen. Examples of the monovalent functional group of elements is nitrogen binding to the silicon element isocyanate group, an amino group, a dialkylamino group, an isothiocyanate group, an azide group, an acetamide _{group, -N (CH 3) C (} O) CH 3, _{-N (CH 3) C (O} ) CF 3, -N = C (CH 3) OSi (CH 3) 3, -N = C (CF 3) OSi (CH 3) 3, -NHC (O) -OSi _{(CH 3) 3, -NHC (} O) -NH-Si (CH 3) 3, an imidazole ring, the oxazolidinone ring, a morpholine ring, -NH-C (O) -Si (CH 3) 3, - _{N (H) 2-i (} Si (H) j R 19 3-j) i (R 19 has any or all of the hydrogen atom of a monovalent hydrocarbon group having the carbon number of which is optionally substituted by a fluorine element group 1 to 18, i is 1 or 2, and j is an integer of 0 to 2).

As the silicon compound D of the formula [16], for example _{(CH 3) 3 SiNH 2,} C 4 H 9 Si (CH 3) 2 NH 2, C 6 H 13 Si (CH 3) 2 NH 2, C 8 _{H 17 Si (CH 3) 2} NH 2, C 10 H 21 Si (CH 3) 2 NH 2, C 12 H 25 Si (CH 3) 2 NH 2, (CH 3) 2 Si (H) amino NH ₂ Silane or an amino group (-NH ₂ group) of the aminosilane is reacted with -N═C═O, -N (CH ₃ ) ₂ , -N (C ₂ H ₅ ) ₂ , -N═C═S, -N _{3, -NHC (O) CH 3} , -N (CH 3) C (O) CH 3, -N (CH 3) C (O) CF 3, -N = C (CH 3) OSi (CH 3) 3 _{, -N = C (CF 3)} OSi (CH 3) 3, -NHC (O) -OSi (CH 3) 3, -NHC (O) -NH-Si (CH 3) 3, an imidazole ring, oxazolidin dinon ring, a morpholine ring, -NH-C (O) -Si (CH 3) 3, -NH-Si (CH 3) 3, -NH-Si (H) (CH 3) 2, -NH-Si ( _{CH 3) 2 (C 4 H} 9), -NH-Si (CH 3) 2 (C 6 H 13), -NH-Si (CH 3) 2 (C 8 H 17), -NH-Si (CH 3 ) ₂ (C ₁₀ H ₂₁ ), -NH-Si (CH ₃ ) ₂ (C ₁₂ H ₂₅ ), -NH-Si (CH ₃ ) ₂ (C ₂ H ₄ C ₆ F ₁₃ ) (CH ₃ ) ₃ } ₂ , and the like.

Among them, the silicon compound D of the formula [16] is preferably the silicon compound A.

In the above water-repellent chemical solution for silicon wafers, the concentration of the silicon compound B is preferably 0.01 to 20% by mass based on 100% by mass of the total amount of the silicon compound A. If the concentration is too low, the effect of the silicon compound B is low. Therefore, even if the concentration is excessively high, the effect of the silicon compound B is not improved, and on the contrary, there is a possibility that the silicon-based wafer surface is eroded. Therefore, the concentration of the silicon compound B is particularly preferably 0.05 to 15% by mass based on 100% by mass of the total amount of the silicon compound A.

In the above water-repellent chemical solution for a silicon wafer, the silicon compound A and the silicon compound B may be diluted with an organic solvent. When the total amount of the silicon compound A and the silicon compound B to be added is in the range of 0.1 to 100 mass% based on 100 mass% of the total amount of the water repellent chemical solution for silicon wafer, the water repellent film Since it is easy to form the film. If it is less than 0.1% by mass, the protective effect of the uneven pattern tends to become insufficient. More preferably, it is 0.5 to 50 mass%, and more preferably 1 to 30 mass%. When the water-repellent chemical solution for a silicon wafer is diluted with an organic solvent, it may contain a low boiling point organic solvent. However, among the components contained in the water-repellent chemical solution for the silicon wafer, It is important that the boiling point of many of these components is above 40 ° C. More preferably, the boiling point is higher than 60 ° C, more preferably higher than 80 ° C.

Examples of the organic solvent which may be used for dilution in the water-repellent chemical solution for silicon wafers include hydrocarbons, esters, ethers, ketones, halogen element-containing solvents, sulfoxide-based solvents, Solvent, a polyvalent alcohol derivative having no OH group, an organic solvent such as a nitrogen-containing solvent having no NH group, or a mixture thereof is suitably used. Among them, the use of a mixture of hydrocarbons, esters, ethers, halogen element-containing solvents, polyhydric alcohol derivatives having no OH group or a mixture thereof can form a water repellent film on the surface of the relief pattern in a short time, desirable.

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. Examples of the ethers include diethyl ether, Examples of the ketones include acetone, acetyl acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone, isophorone, and the like. Examples of the halogen element-containing solvent include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane and hexafluorobenzene, 1,1,1,3,3-penta Hydrofluorocarbons such as fluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane and ZEORORA-H (manufactured by ZEON CORPORATION) Methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, ASAHIKLIN AE-3000 (manufactured by Asahi Glass Co., Ltd.), and the like. , Hydrofluoroethers such as Novec7100, Novec7200, Novec7300 and Novec7600 (all available from 3M Limited), chlorocarbons such as tetrachloromethane and the like, hydrochlorocarbons such as chloroform, dichlorodifluoromethane Dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1 -Chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene and the like, perfluoroether, perfluoropolyether And examples of the sulfoxide-based solvent include dimethylsulfoxide, and examples of the lactone-based solvent include γ-butyrolactone, γ-butyrolactone, γ-valerolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, Dodecanolactone, dodecanolactone, dodecanolactone, delta-valerolactone, delta-hexanolactone, delta-octanolactone, delta-nonanolactone, delta-decanolactone, delta-undecanolactone, And examples of the carbonate-based solvent include dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, and propylene carbonate. Examples of the polyhydric alcohol derivative having no OH group include ethylene glycol dimethyl ether, ethylene glycol diethyl ether , Ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene Diethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diisobutyl ether, diethylene glycol diisobutyl ether, Diethylene glycol diethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, tri Ethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetra Tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol diacetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, Propylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol di Tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol mono Methylene ether acetate, tetrapropylene glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, and glycerin triacetate. Examples of the nitrogen-containing solvent having no NH group include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, triethylamine, pyridine and the like.

The use of a non-flammable solvent for part or all of the above solvents is preferable because the water-repellent chemical solution for silicon-based wafers becomes incombustible or has a high flash point, thereby reducing the risk of the water-repellent chemical solution for the silicon-based wafers. The halogen-containing solvent is often nonflammable, and a nonflammable halogen-containing solvent can be suitably used as an incombustible organic solvent.

It is preferable to use a solvent having a flash point exceeding 70 캜 as the solvent from the viewpoint of safety in the fire fighting method.

Further, according to the "International harmonization system for classification and labeling of chemicals: GHS", a solvent having a flash point of 93 ° C or lower is defined as a "flammable liquid". Therefore, even if the solvent is not a nonflammable solvent, if a solvent having a flash point exceeding 93 ° C. is used as the solvent, the above-mentioned water-repellent chemical easily tends to have a flash point exceeding 93 ° C. and the chemical becomes less likely to be a "flammable liquid" .

A lactone-based solvent, a carbonate-based solvent, or a derivative of a polyhydric alcohol that does not have an OH group is preferred because it has a high flash point so that the risk of a water-repellent chemical solution for silicon-based wafers can be reduced. Specifically, from the viewpoint of the above safety, it is preferable to use at least one of γ-butyrolactone, γ-valerolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ- Nanolactone,? -Decanolactone,? -Undecanolactone,? -Decenoolactone,? -Valerolactone,? -Hexanolactone,? -Octanolactone,? -Nonanolactone, , δ-undecanolactone, δ-dodecanolactone, ε-hexanolactone, propylene carbonate, ethylene glycol dibutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol ethyl methyl ether, diethylene glycol Diethylene glycol monobutyl ether acetate, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, Glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, tri But are not limited to, ethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, Ethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol methyl propyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dip Dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monoethyl ether acetate, Tripropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol diacetate, glycerin triacetate and the like are used as the above-mentioned solvents, And more preferably at least one of? -Butyrolactone,? -Hexanolactone,? -Heptanolactone,? -Octanolactone,? -Nonanolactone,? -Decanolactone,? - Undecanolactone,? -Dodecanolactone,? -Valero Octanoactone, 隆 -hexanolactone, 隆 -hexanolactone, 隆 -octanolactone, 隆 -hexanolactone, 隆 -hexanolactone, 隆 -hexanolactone, 隆 -dactanolactone, Acetate, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol dimethyl Ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol Diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol Tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol Diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol Monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol And methyl ether, tetrapropylene glycol monomethyl ether acetate, tetraethylene glycol diacetate, butylene glycol diacetate, glycerol triacetate is more preferably used as the solvent.

In the above water-repellent chemical solution for a silicon wafer, it is preferable that the total amount of water in the starting material is 5,000 mass ppm or less based on the total amount of the raw materials. When the total amount of water exceeds 5000 mass ppm, the effect of the silicon compound A is lowered, and it becomes difficult to form the water repellent coating in a short time. Therefore, the water content in the starting material of the water repellent chemical for the silicon-based wafer is preferably as small as possible, more preferably 1000 mass ppm or less, further preferably 500 mass ppm or less. The water content in the starting material of the water repellent chemical for the silicon wafer may be 5 ppm by mass or more if it is within the above range.

Hereinafter, the second method will be described. The water repellent chemical solution for a metal-based wafer includes at least one compound selected from the compounds represented by the above general formulas [6] to [12] and salt compounds thereof, and a solvent.

The hydrocarbon group represented by R ⁸ in the general formula [6] includes, for example, an alkyl group, an alkylene group, or a part or all of hydrogen atoms thereof substituted with a fluorine element.

The hydrocarbon group contained in R ⁹ in the general formula [6] includes, for example, an alkyl group, an alkylene group, or a part or all of hydrogen atoms thereof substituted with a fluorine element. It is also preferable that -OR ²² (R ²² is a hydrocarbon group having 1 to 18 carbon atoms). The carbon number of R ²² is preferably from 1 to 8, more preferably from 1 to 4, because it can give better water repellency. R ²² is preferably a linear alkyl group.

Examples of the element-containing compound of the general formula [6], for example, _{CH 3 P (O) (OH} ) 2, C 2 H 5 P (O) (OH) 2, C 3 H 7 P (O) (OH _{) 2, C 4 H 9 P} (O) (OH) 2, C 5 H 11 P (O) (OH) 2, C 6 H 13 P (O) (OH) 2, C 7 H 15 P (O) _{(OH) 2, C 8 H} 17 P (O) (OH) 2, C 9 H 19 P (O) (OH) 2, C 10 H 21 P (O) (OH) 2, C 11 H 23 P ( _{O) (OH) 2, C} 12 H 25 P (O) (OH) 2, C 13 H 27 P (O) (OH) 2, C 14 H 29 P (O) (OH) 2, C 15 H 31 _{P (O) (OH) 2} , C 16 H 33 P (O) (OH) 2, C 17 H 35 P (O) (OH) 2, C 18 H 37 P (O) (OH) 2, C 6 _{H 5 P (O) (OH} ) 2, CF 3 P (O) (OH) 2, C 2 F 5 P (O) (OH) 2, C 3 F 7 P (O) (OH) 2, C 4 _{F 9 P (O) (OH} ) 2, C 5 F 11 P (O) (OH) 2, C 6 F 13 P (O) (OH) 2, C 7 F 15 P (O) (OH) 2, _{C 8 F 17 P (O)} (OH) 2, CF 3 C 2 H 4 P (O) (OH) 2, C 2 F 5 C 2 H 4 P (O) (OH) 2, C 3 F 7 C _{2 H 4 P (O) (} OH) 2, C 4 F 9 C 2 H 4 P (O) (OH) 2, C 5 F 11 C 2 H 4 P (O) (OH) 2, C 6 F 13 _{C 2 H 4 P (O)} (OH) 2, C 7 F 15 C 2 H 4 P (O) (OH) 2, C 8 F 17 C 2 H 4 P (O) (OH) 2, or the compound of -P (O) (OH) ₂ group -P (O) (OH) OCH 3 group, -P (O) (OH) OC 2 H 5 _{group, -P (O) (OCH 3} ) ₂ groups, and -P (O) (OC ₂ H ₅ ) ₂ groups.

The phosphorus atom-containing compound of the above general formula [6] can give better water repellency, so that g in the general formula [6] is preferably 1 or 2, more preferably 2 or 3, Is preferably a compound represented by [17].

R ²³ -P (= O) (OH) ₂ [17]

(In the formula [17], R < ²³ > is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms.)

R ^{8 in} the general formula [6] and R ²³ in the general formula [17] are, for example, those obtained by substituting the hydrogen atom of the alkyl group, phenyl group or phenyl group with an alkyl group, a naphthyl group, and a part or all of the hydrocarbon groups And those in which the hydrogen element is substituted by a fluorine element.

R ^{8 in} the general formula [6] and R ²³ in the general formula [17] have a carbon number of 2 to 16, especially 4 to 14, more preferably 6 to 14, Do. The hydrocarbon group in which some or all of the hydrogen atoms may be substituted with a fluorine element is preferably an alkyl group, and particularly preferably a straight chain alkyl group. When the hydrocarbon group is a straight chain alkyl group, R ⁸ and R ²³ , which are the hydrophobic moieties of the phosphorus-containing compounds represented by the general formulas [6] and [17], form a water repellent coating film in a direction perpendicular to the surface of the water- It is more preferable that the effect of imparting water repellency is enhanced because it is liable to be placed side by side. In addition, since R ⁸ and R ²³ can give better water repellency, hydrocarbon groups in which some or all hydrogen elements are substituted with fluorine atoms are obtained.

The phosphorus-containing compound may be present in the salt of the general formula [6] or [17]. Examples of the salt include an ammonium salt and an amine salt.

Further, in the general formula [7] of the R ^10, the general formula [8] of the R ^11, the general formula [9] of the R ^14, represented by the general formula [10] R ^15, general formula [11] R ^16, and general R ¹⁷ and R ¹⁸ of formula [12], some or all of the hydrogen atom is a carbon atoms which may be substituted with a fluorine element is preferably a 1 to 18 monovalent hydrocarbon, and _{C m H 2m +1 (m =} 1~ (N = 1 to 8), C _r F _{2r + 1} CH ₂ (r = 1 to 8), C _s F _{2s + 1} (s = 1 to 8), C _n F _{2n +1} CH ₂ CH ₂ .

As the compound represented by the general formula [7], for example, _{CH 3 COCl, C 2 H 5} COCl, C 3 H 7 COCl, C 4 H 9 COCl, C 5 H 11 COCl, C 6 H 13 COCl, C _{7 H 15 COCl, C 8 H} 17 COCl, C 9 H 19 COCl, C 10 H 21 COCl, C 11 H 23 COCl, C 12 H 25 COCl, C 13 H 27 COCl, C 14 H 29 COCl, C 15 H _{31 COCl, C 16 H 33 COCl} , C 17 H 35 COCl, C 18 H 37 COCl, C 6 H 5 COCl, CF 3 COCl, C 2 F 5 COCl, C 3 F 7 COCl, C 4 F 9 COCl, C ₅ F ₁₁ COCl, C ₆ F ₁₃ COCl, C ₇ F ₁₅ COCl, C ₈ F ₁₇ COCl, or compounds in which the -Cl group is substituted with -F group, -Br group or -I group.

It is among the above compounds, in consideration of the affinity, and a metal-based water-repellent given to the wafer surface effects on material comprising a metallic element, in particular preferred, for example _{C 8 H 17 COCl, C 9} H 19 COCl, C 10 _{H 21 COCl, C 11 H 23} COCl, C 12 H 25 COCl, C 13 H 27 COCl, C 14 H 29 COCl, C 15 H 31 COCl, C 16 H 33 COCl, C 17 H 35 COCl, C 18 H 37 COCl, C ₄ F ₉ COCl, C ₅ F ₁₁ COCl, C ₆ F ₁₃ COCl, C ₇ F ₁₅ COCl, and C ₈ F ₁₇ COCl.

Examples of the compound represented by the general formula [8] include C ₅ H ₁₁ NH ₂ , C ₆ H ₁₃ NH ₂ , C ₇ H ₁₅ NH ₂ , C ₈ H ₁₇ NH ₂ , C ₉ H ₁₉ NH ₂ , C ₁₀ H ₂₁ NH ₂ , C ₁₁ H ₂₃ NH ₂ , C ₁₂ H ₂₅ NH ₂ , C ₁₃ H ₂₇ NH ₂ , C ₁₄ H ₂₉ NH ₂ , C ₁₅ H ₃₁ NH ₂ , C ₁₆ H ₃₃ NH ₂ , C _{17 H 35 NH 2, C 18} H 37 NH 2, CF 3 NH 2, CF 3 C 2 H 4 NH 2, C 2 F 5 NH 2, C 2 F 5 C 2 H 4 NH 2, C 3 F 7 NH _{2, C 3 F 7 C 2} H 4 NH 2, C 4 F 9 NH 2, C 4 F 9 C 2 H 4 NH 2, C 4 F 9 CH 2 NH 2, C 5 F 11 NH 2, C 5 F _{11 C 2 H 4 NH 2,} C 5 F 11 CH 2 NH 2, C 6 F 13 NH 2, C 6 F 13 C 2 H 4 NH 2, C 6 F 13 CH 2 NH 2, C 7 F 15 NH 2 _{, C 7 F 15 C 2 H} 4 NH 2, C 7 F 15 CH 2 NH 2, C 8 F 17 NH 2, C 8 F 17 C 2 H 4 NH 2, C 8 F 17 CH 2 NH 2, C 4 _{F 7 H 2 NH 2, C} 6 F 11 H 2 NH 2, C 8 F 15 H 2 NH 2, (C 3 H 7) 2 NH, (C 4 H 9) 2 NH, (C 5 H 11) 2 _{NH, (C 6 H 13)} 2 NH, (C 7 H 15) 2 NH, (C 8 H 17) 2 NH, (C 9 H 19) 2 NH, (C 10 H 21) 2 NH, (C 11 _{H 23) 2 NH, (C} 12 H 25) 2 NH, (C 13 H 27) 2 NH, (C 14 H 29) 2 NH, (C _{15 H 31) 2 NH, (} C 16 H 33) 2 NH, (C 17 H 35) 2 NH, (C 18 H 37) 2 NH, (CF 3) 2 NH, (C 2 F 5) 2 NH, _{(C 3 F 7) 2 NH} , (C 4 F 9) 2 NH, (C 5 F 11) 2 NH, (C 6 F 13) 2 NH, (C 7 F 15) 2 NH, (C 8 F 17 _{) 2 NH, (C 4 F} 7 H 2) 2 NH, (C 6 F 11 H 2) 2 NH, (C 8 F 15 H 2) 2 NH, (C 2 H 5) 3 N, (C 3 H _{7) 3 N, (C 4} H 9) 3 N, (C 5 H 11) 3 N, (C 6 H 13) 3 N, (C 7 H 15) 3 N, (C 8 H 17) 3 N, _{(C 9 H 19) 3 N} , (C 10 H 21) 3 N, (C 11 H 23) 3 N, (C 12 H 25) 3 N, (C 13 H 27) 3 N, (C 14 H 29 _{) 3 N, (C 15 H} 31) 3 N, (C 16 H 33) 3 N, (C 17 H 35) 3 N, (C 18 H 37) 3 N, (CF 3) 3 N, (C 2 _{F 5) 3 N, (C} 3 F 7) 3 N, (C 4 F 9) 3 N, (C 5 F 11) 3 N, (C 6 F 13) 3 N, (C 7 F 15) 3 N _{, (C 8 F 17) 3} N, (C 4 F 7 H 2) 3 N, (C 6 F 11 H 2) 3 N, (C 8 F 15 H 2) 3 N, (C 5 H 11) ( _{CH 3) NH, (C 6} H 13) (CH 3) NH, (C 7 H 15) (CH 3) NH, (C 8 H 17) (CH 3) NH, (C 9 H 19) (CH 3 _{) NH, (C 10 H 21} ) (CH 3) NH, (C 11 H 23) (CH 3) NH, (C 12 H 25) (CH 3) NH, (C 13 H 27) (CH 3) NH , (C ₁₄ H ₂₉ ) (CH ₃ ) NH, (C ₁₅ H ₃₁ ) ( _{CH 3) NH, (C 16} H 33) (CH 3) NH, (C 17 H 35) (CH 3) NH, (C 18 H 37) (CH 3) NH, (CF 3) (CH 3) NH _{, (C 2 F 5) (} CH 3) NH, (C 3 F 7) (CH 3) NH, (C 4 F 9) (CH 3) NH, (C 5 F 11) (CH 3) NH, ( _{C 6 F 13) (CH 3} ) NH, (C 7 F 15) (CH 3) NH, (C 8 F 17) (CH 3) NH, (C 3 H 7) (CH 3) 2 N, (C _{4 H 9) (CH 3)} 2 N, (C 5 H 11) (CH 3) 2 N, (C 6 H 13) (CH 3) 2 N, (C 7 H 15) (CH 3) 2 N, _{(C 8 H 17) (CH} 3) 2 N, (C 9 H 19) (CH 3) 2 N, (C 10 H 21) (CH 3) 2 N, (C 11 H 23) (CH 3) 2 _{N, (C 12 H 25)} (CH 3) 2 N, (C 13 H 27) (CH 3) 2 N, (C 14 H 29) (CH 3) 2 N, (C 15 H 31) (CH 3 _{) 2 N, (C 16 H} 33) (CH 3) 2 N, (C 17 H 35) (CH 3) 2 N, (C 18 H 37) (CH 3) 2 N, (CF 3) (CH 3 _{) 2 N, (C 2 F} 5) (CH 3) 2 N, (C 3 F 7) (CH 3) 2 N, (C 4 F 9) (CH 3) 2 N, (C 5 F 11) ( _{CH 3) 2 N, (C} 6 F 13) (CH 3) 2 N, (C 7 F 15) (CH 3) 2 N, (C 8 F 17) (CH 3) include compounds such as ₂ N have. The compound represented by the above general formula [8] may be used as a salt. Examples of the salt include inorganic acid salts such as carbonate, hydrochloride, sulfate and nitrate, and organic acid salts such as acetate, propionate, butyrate and phthalate.

Particularly preferable among the above compounds in consideration of the affinity to a substance containing a metal element and the effect of imparting water repellency to the surface of a metal-based wafer are C ₆ H ₁₃ NH ₂ , C ₇ H ₁₅ NH ₂ , C ₈ H ₁₇ NH ₂ , C ₉ H ₁₉ NH ₂ , C ₁₀ H ₂₁ NH ₂ , C ₁₁ H ₂₃ NH ₂ , C ₁₂ H ₂₅ NH ₂ , C ₁₃ H ₂₇ NH ₂ , C ₁₄ H ₂₉ NH ₂ , C _{15 H 31 NH 2, C 16} H 33 NH 2, C 17 H 35 NH 2, C 18 H 37 NH 2, (C 4 H 9) 2 NH, (C 5 H 11) 2 NH, (C 6 H 13 _{) 2 NH, (C 7 H} 15) 2 NH, (C 8 H 17) 2 NH, (C 9 H 19) 2 NH, (C 10 H 21) 2 NH, (C 11 H 23) 2 NH, ( _{C 12 H 25) 2 NH,} (C 13 H 27) 2 NH, (C 14 H 29) 2 NH, (C 15 H 31) 2 NH, (C 16 H 33) 2 NH, (C 17 H 35) _{2 NH, (C 18 H 37} ) 2 NH, (C 4 H 9) 3 N, (C 5 H 11) 3 N, (C 6 H 13) 3 N, (C 7 H 15) 3 N, (C _{8 H 17) 3 N, (} C 9 H 19) 3 N, (C 10 H 21) 3 N, (C 11 H 23) 3 N, (C 12 H 25) 3 N, (C 13 H 27) 3 _{N, (C 14 H 29)} 3 N, (C 15 H 31) 3 N, (C 16 H 33) 3 N, (C 17 H 35) 3 N, (C 18 H 37) 3 N, (C 5 H ₁₁ ) (CH ₃ ) NH, (C _{6 H 13) (CH 3) NH} , (C 7 H 15) (CH 3) NH, (C 8 H 17) (CH 3) NH, (C 9 H 19) (CH 3) NH, (C 10 H 21 _{) (CH 3) NH, (} C 11 H 23) (CH 3) NH, (C 12 H 25) (CH 3) NH, (C 13 H 27) (CH 3) NH, (C 14 H 29) ( _{CH 3) NH, (C 15} H 31) (CH 3) NH, (C 16 H 33) (CH 3) NH, (C 17 H 35) (CH 3) NH, (C 18 H 37) (CH 3 _{) NH, (C 4 H 9} ) (CH 3) 2 N, (C 5 H 11) (CH 3) 2 N, (C 6 H 13) (CH 3) 2 N, (C 7 H 15) (CH _{3) 2 N, (C 8} H 17) (CH 3) 2 N, (C 9 H 19) (CH 3) 2 N, (C 10 H 21) (CH 3) 2 N, (C 11 H 23) _{(CH 3) 2 N, (} C 12 H 25) (CH 3) 2 N, (C 13 H 27) (CH 3) 2 N, (C 14 H 29) (CH 3) 2 N, (C 15 H _{31) (CH 3) 2 N} , (C 16 H 33) (CH 3) 2 N, (C 17 H 35) (CH 3) 2 N, (C 18 H 37) (CH 3) 2 N, C 4 F ₉ NH ₂ , C ₄ F ₉ C ₂ H ₄ NH ₂ , C ₄ F ₉ CH ₂ NH ₂ , C ₅ F ₁₁ NH ₂ , C ₅ F ₁₁ C ₂ H ₄ NH ₂ , C ₅ F ₁₁ CH ₂ NH _{2, C 6 F 13 NH 2} , C 6 F 13 C 2 H 4 NH 2, C 6 F 13 CH 2 NH 2, C 7 F 15 NH 2, C 7 F 15 C 2 H 4 NH 2, C 7 F ₁₅ CH ₂ NH ₂ , C ₈ F ₁₇ NH ₂ , C ₈ F ₁₇ C ₂ H ₄ NH ₂ , and C ₈ F ₁₇ CH ₂ NH ₂ .

Examples of the compound represented by the above general formula [9] include C ₅ H ₁₁ COOH, C ₆ H ₁₃ COOH, C ₇ H ₁₅ COOH, C ₈ H ₁₇ COOH, C ₉ H ₁₉ COOH, C ₁₀ H ₂₁ COOH , C ₁₁ H ₂₃ COOH, C ₁₂ H ₂₅ COOH, C ₁₃ H ₂₇ COOH, C ₁₄ H ₂₉ COOH, C ₁₅ H ₃₁ COOH, C ₁₆ H ₃₃ COOH, C ₁₇ H ₃₅ COOH, C ₁₈ H ₃₇ COOH, C ₆ H ₅ COOH, C ₅ F ₁₁ COOH, C ₆ F ₁₃ COOH, C ₇ F ₁₅ COOH, and C ₈ F ₁₇ COOH, or a compound in which the -COOH group of the compound is replaced by -COOCH ₃ group, -COOC ₂ H ₅ Group, -COOC ₆ H ₅ group, -COSH group, and -COSCH ₃ group.

Of the above compounds, particularly preferable ones are C ₅ H ₁₁ COOH, C ₆ H ₁₃ COOH, C ₇ H ₇ COOH, C ₆ H ₁₃ COOH, and C ₆ H ₁₃ COOH, in consideration of the affinity to a substance containing a metal element and the effect of imparting water repellency to the surface of a metal- _{H 15 COOH, C 8 H 17} COOH, C 9 H 19 COOH, C 10 H 21 COOH, C 11 H 23 COOH, C 12 H 25 COOH, C 13 H 27 COOH, C 14 H 29 COOH, C 15 H 31 COOH, C ₁₆ H ₃₃ COOH, C ₁₇ H ₃₅ COOH, C ₁₈ H ₃₇ COOH, or the -COOH group of the compound, the -COOCH ₃ group, the -COOC ₂ H ₅ group, the -COOC ₆ H ₅ group, the -COSH group , Compounds substituted with -COSCH ₃ groups, and the like.

Examples of the compound represented by the general formula [10] include C ₂ H ₅ NCO, C ₃ H ₇ NCO, C ₄ H ₉ NCO, C ₅ H ₁₁ NCO, C ₆ H ₁₃ NCO, C ₇ H ₁₅ NCO _{, C 8 H 17 NCO, C} 9 H 19 NCO, C 10 H 21 NCO, C 11 H 23 NCO, C 12 H 25 NCO, C 13 H 27 NCO, C 14 H 29 NCO, C 15 H 31 NCO, C ₁₆ H ₃₃ NCO, C ₁₇ H ₃₅ NCO, C ₁₈ H ₃₇ NCO, CF ₃ NCO, CF ₃ CH ₂ NCO, CF ₃ C ₂ H ₄ NCO, C ₂ F ₅ NCO, C ₂ F ₅ CH ₂ NCO, C _{2 F 5 C 2 H 4 NCO} , C 3 F 7 NCO, C 3 F 7 CH 2 NCO, C 3 F 7 C 2 H 4 NCO, C 4 F 9 NCO, C 4 F 9 CH 2 NCO, C 4 F _{9 C 2 H 4 NCO, C} 5 F 11 NCO, C 5 F 11 CH 2 NCO, C 5 F 11 C 2 H 4 NCO, C 6 F 13 NCO, C 6 F 13 CH 2 NCO, C 6 F 13 C ₂ H ₄ NCO, C ₇ F ₁₅ NCO, C ₇ F ₁₅ CH ₂ NCO, C ₇ F ₁₅ C ₂ H ₄ NCO, C ₈ F ₁₇ NCO, C ₈ F ₁₇ CH ₂ NCO, C ₈ F ₁₇ C ₂ H _{4 NCO, C 2 H 4 (} NCO) 2, C 3 H 6 (NCO) 2, C 4 H 8 (NCO) 2, C 5 H 10 (NCO) 2, C 6 H 12 (NCO) 2, C 7 _{H 14 (NCO) 2, C} 8 H 16 (NCO) 2, C 9 H 18 (NCO) 2, C 10 H 20 (NCO) 2, C 11 H 22 (NCO) 2, C 12 H 24 (NCO) ₂ , C ₁₃ H ₂₆ (NCO) ₂ , C ₁₄ H ₂₈ (NCO) ₂ , C ₁₅ H _{30 (NCO) 2, C 16} H 32 (NCO) 2, C 17 H 34 (NCO) 2, C 18 H 36 (NCO) 2, (NCO) C 2 H 4 NCO, (NCO) C 3 H 6 NCO _{, (NCO) C 4 H 8} NCO, (NCO) C 5 H 10 NCO, (NCO) C 6 H 12 NCO, (NCO) C 7 H 14 NCO, (NCO) C 8 H 16 NCO, (NCO) C _{9 H 18 NCO, (NCO)} C 10 H 20 NCO, (NCO) C 11 H 22 NCO, (NCO) C 12 H 24 NCO, (NCO) C 13 H 26 NCO, (NCO) C 14 H 28 NCO, _{(NCO) C 15 H 30 NCO} , (NCO) C 16 H 32 NCO, (NCO) C 17 H 34 NCO, (NCO) C 18 H 36 NCO, C 2 H 3 (NCO) 3, C 3 H 5 ( _{NCO) 3, C 4 H 7} (NCO) 3, C 5 H 9 (NCO) 3, C 6 H 11 (NCO) 3, C 7 H 13 (NCO) 3, C 8 H 15 (NCO) 3, C _{9 H 17 (NCO) 3,} C 10 H 19 (NCO) 3, C 11 H 21 (NCO) 3, C 12 H 23 (NCO) 3, C 13 H 25 (NCO) 3, C 14 H 27 (NCO _{) 3, C 15 H 29 (} NCO) 3, C 16 H 31 (NCO) 3, C 17 H 33 (NCO) 3, C 18 H 35 (NCO) 3, C (NCO) 4, (NCO) 2 C _{2 H 2 (NCO) 2,} (NCO) 2 C 3 H 4 (NCO) 2, (NCO) 2 C 4 H 6 (NCO) 2, (NCO) 2 C 5 H 8 (NCO) 2, (NCO) _{2 C 6 H 10 (NCO)} 2, (NCO) 2 C 7 H 12 (NCO) 2, (NCO) 2 C 8 H 14 (NCO) 2, (NCO) 2 C 9 H 16 (NCO) 2, ( NCO) ₂ C ₁₀ H ₁₈ (NCO) ₂ , (NCO) ₂ C ₁₁ H ₂₀ ( _{NCO) 2, (NCO) 2} C 12 H 22 (NCO) 2, (NCO) 2 C 13 H 24 (NCO) 2, (NCO) 2 C 14 H 26 (NCO) 2, (NCO) 2 C 15 H _{28 (NCO) 2, (NCO} ) 2 C 16 H 30 (NCO) 2, (NCO) 2 C 17 H 32 (NCO) 2, (NCO) 2 C 18 H 34 (NCO) isocyanate compound in the _second place, or A compound in which the isocyanate group (-NCO group) of the isocyanate compound is substituted with a cyclic structure including a nitrogen element such as -SH group, -CHO group, -CONHOH group, imidazoline ring (the following formula [18] .

Of the above compounds, particularly preferred are C ₄ H ₉ NCO, C ₅ H ₁₁ NCO, C ₆ H ₉ NCO, and the like, in consideration of the affinity to a substance containing a metal element and the effect of imparting water repellency to the surface of a metal- _{H 13 NCO, C 7 H 15} NCO, C 8 H 17 NCO, C 9 H 19 NCO, C 10 H 21 NCO, C 11 H 23 NCO, C 12 H 25 NCO, C 13 H 27 NCO, C 14 H 29 _{NCO, C 15 H 31 NCO,} C 16 H 33 NCO, C 17 H 35 NCO, C 18 H 37 NCO, C 3 F 7 CH 2 NCO, C 3 F 7 C 2 H 4 NCO, C 4 F 9 NCO, _{C 4 F 9 CH 2 NCO,} C 4 F 9 C 2 H 4 NCO, C 5 F 11 NCO, C 5 F 11 CH 2 NCO, C 5 F 11 C 2 H 4 NCO, C 6 F 13 NCO, C 6 _{F 13 CH 2 NCO, C 6} F 13 C 2 H 4 NCO, C 7 F 15 NCO, C 7 F 15 CH 2 NCO, C 7 F 15 C 2 H 4 NCO, C 8 F 17 NCO, C 8 F 17 CH ₂ NCO and C ₈ F ₁₇ C ₂ H ₄ NCO, or an isocyanate group (-NCO group) of the isocyanate compound with an isocyanate group such as -SH group, -CHO group, -CONHOH group or imidazoline ring Compounds substituted with a ring structure containing a nitrogen element, etc. The can.

Examples of the compound represented by the above general formula [11] include C ₄ H ₄ S, CH ₃ C ₄ H ₃ S, C ₂ H ₅ C ₄ H ₃ S, C ₃ H ₇ C ₄ H ₃ S, C ₄ H ₉ C ₄ H ₃ S, C ₅ H ₁₁ C ₄ H ₃ S, C ₆ H ₁₃ C ₄ H ₃ S, C ₇ H ₁₅ C ₄ H ₃ S, C ₈ H ₁₇ C ₄ H ₃ S, C ₉ H ₁₉ C ₄ H ₃ S, C ₁₀ H ₂₁ C ₄ H ₃ S, C ₁₁ H ₂₃ C ₄ H ₃ S, C ₁₂ H ₂₅ C ₄ H ₃ S, C ₁₃ H ₂₇ C ₄ H ₃ S, C ₁₄ H ₂₉ C ₄ H ₃ S, C ₁₅ H ₃₁ C ₄ H ₃ S, C ₁₆ H ₃₃ C ₄ H ₃ S, C ₁₇ H ₃₅ C ₄ H ₃ S, C ₁₈ H ₃₇ C ₄ H ₃ S, C ₃ H ₃ NS, CH ₃ C ₃ H ₂ NS, C ₂ H ₅ C ₃ H ₂ NS, C ₃ H ₇ C ₃ H ₂ NS, C ₄ H ₉ C ₃ H ₂ NS, C ₅ H ₁₁ C ₃ H ₂ NS, C ₆ H ₁₃ C ₃ H ₂ NS, C ₇ H ₁₅ C ₃ H ₂ NS, C ₈ H ₁₇ C ₃ H ₂ NS, C ₉ H ₁₉ C ₃ H ₂ NS, C ₁₀ H ₂₁ C ₃ H ₂ NS, C ₁₁ H ₂₃ C ₃ H ₂ NS, C ₁₂ H ₂₅ C ₃ H ₂ NS, C ₁₃ H ₂₇ C ₃ H ₂ NS, C ₁₄ H ₂₉ C ₃ H ₂ NS, C ₁₅ H ₃₁ C ₃ H ₂ NS, C ₁₆ H ₃₃ C ₃ H ₂ NS, C ₁₇ H ₃₅ C ₃ H ₂ NS and C ₁₈ H ₃₇ C ₃ H ₂ NS. C ₄ H ₄ S is thiophene, C ₄ H ₃ S is thiophene ring, C ₃ H ₃ NS is thiazole and C ₃ H ₂ NS is thiazole ring.

Examples of the compound represented by the above general formula [12] include CH ₃ COOCOCH ₃ , C ₂ H ₅ COOCOC ₂ H ₅ , C ₃ H ₇ COOCOC ₃ H ₇ , C ₄ H ₉ COOCOC ₄ H ₉ , C ₅ H ₁₁ COOCOC ₅ H ₁₁ , C ₆ H ₁₃ COOCOC ₆ H ₁₃ , C ₇ H ₁₅ COOCOC ₇ H ₁₅ , C ₈ H ₁₇ COOCOC ₈ H ₁₇ , C ₉ H ₁₉ COOCOC ₉ H ₁₉ , C ₁₀ H ₂₁ COOCOC ₁₀ H ₂₁ , C ₁₁ H ₂₃ COOCOC ₁₁ H ₂₃ , C ₁₂ H ₂₅ COOCOC ₁₂ H ₂₅ , C ₁₃ H ₂₇ COOCOC ₁₃ H ₂₇ , C ₁₄ H ₂₉ COOCOC ₁₄ H ₂₉ , C ₁₅ H ₃₁ COOCOC ₁₅ H ₃₁ , C ₁₆ H _{33 COOCOC 16 H 33, C 17 H} 35 COOCOC 17 H 35, C 18 H 37 COOCOC 18 H 37, C 6 H 5 COOCOC 6 H 5, CF 3 COOCOCF 3, C 2 F 5 COOCOC 2 F 5, C 3 F 7 _{COOCOC 3 F 7, C 4 F} 9 COOCOC 4 F 9, C 5 F 11 COOCOC 5 F 11, C 6 F 13 COOCOC 6 F 13, C 7 F 15 COOCOC 7 F 15, C 8 F 17 COOCOC 8 F 17 , etc. ≪ / RTI >

The compound selected from the compounds represented by the above-mentioned general formulas [6] to [12] and the compound selected from the salt compound has an HLB value of 0.001 to 10 according to the Griffin method, .

The compound selected from the compounds represented by the above-mentioned general formulas [6] to [12] and the compound selected from the salt compound can be a compound represented by the following general formula [19] It is preferable because it is possible to give.

R ²⁴ -X ¹¹ [19]

X ¹¹ is selected from the group consisting of -P (O) (OH) ₂ , -NH ₂ group, -N═C═O group, -SH group, -CONHOH group and imidazoline ring And R ²⁴ is a hydrocarbon group having 4 to 18 carbon atoms or a C _t F _{2t +1} - (CH ₂ ) _u - group (t = 4 to 8, u = 0 to 2).

Specifically, the solvent used in the second method of the present invention may be a hydrocarbon, an ester, an ether, a ketone, a halogen element-containing solvent, a sulfoxide-based solvent, a lactone-based solvent, a carbonate- A solvent, a derivative of a polyhydric alcohol having no OH group, a solvent same as a solvent containing a nitrogen element having no NH group, and a solvent such as water, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, Ethylene glycol, 1,3-propanediol, 1,2-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, triethylene glycol, tripropylene glycol, , Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol Tetraethylene glycol monomethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol A derivative of a polyhydric alcohol having an OH group such as monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monomethyl ether and butylene glycol monomethyl ether, a nitrogen element having an NH group such as formamide Containing solvent.

If a part or all of the solvent is nonflammable, the water repellent chemical becomes incombustible, or the flash point becomes high, so that the risk of the chemical is lowered. The halogen-containing solvent is often nonflammable, and a nonflammable halogen-containing solvent can be suitably used as a nonflammable solvent. Water can also be used as a nonflammable solvent.

It is preferable to use a solvent having a flash point exceeding 70 캜 as the solvent from the viewpoint of safety in the fire fighting method.

In addition, according to the "International harmonization system for classification and labeling of chemicals: GHS", a solvent having a flash point of 93 ° C or lower is defined as a "flammable liquid". Therefore, even if the solvent is not a nonflammable solvent, if a solvent having a flash point exceeding 93 ° C. is used as the solvent, the above-mentioned water-repellent chemical easily tends to have a flash point exceeding 93 ° C. and the chemical becomes less likely to be a "flammable liquid" .

In addition, lactone-based solvents, carbonate-based solvents, and derivatives of polyhydric alcohols are preferred because they can lower the risk of the water-repellent chemical solution because many of them have a high flash point. Specifically, from the viewpoint of the safety described above, specifically, a solvent having a flash point of more than 70 캜 described in the first method, or a solvent having a flash point of more than 70 캜 described in the first method or a solvent such as ethylene glycol, diethylene glycol, 1,2- Butylene glycol, triethylene glycol, tetraethylene glycol, tetrapropylene glycol, glycerin, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether , Tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether , Tripropylene glycol monobutyl ether and tetrapropylene glycol monomethyl ether. The solvent is preferably a solvent having a flash point exceeding 93 ° C as described in the first method, or a solvent having a flash point exceeding 93 ° C, such as ethylene glycol, di Ethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, triethylene glycol, tripropylene glycol, , Tetrapropylene glycol, glycerin, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, di Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, Glycol monopropyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol Monobutyl ether, tetrapropyleneglycol monomethyl ether and the like, more preferably a solvent having a flash point exceeding 93 캜.

The concentration of at least one compound selected from the group consisting of the compounds represented by the general formulas [6] to [12] and the salt compounds thereof in the water-repellent chemical solution for a metal-based wafer is preferably such that the total amount of the metal- And preferably 0.0005 to 2% by mass with respect to the mass%. When the amount is less than 0.0005 mass%, the effect of imparting water repellency tends to be insufficient, while when it is more than 2 mass%, it tends to be difficult to dissolve in a solvent. More preferably from 0.001 to 1% by mass, and particularly preferably from 0.0015 to 0.8% by mass. The water-repellent chemical solution for a metal-based wafer may contain an organic solvent having a low boiling point, but it is important that the boiling point of the component having the greatest mass ratio among components contained in the water-repellent chemical solution for the metal-based wafer is more than 40 ° C. More preferably, the boiling point is higher than 60 ° C, more preferably higher than 80 ° C.

As the solvent of the water-repellent chemical solution for metal wafers, water, or a mixture thereof is preferably used as the solvent of the hydrocarbons, esters, ethers, ketones and derivatives of polyhydric alcohols, Do. Further, in consideration of the substitution property with the cleaning liquid, particularly the cleaning liquid comprising an aqueous liquid, derivatives of polyhydric alcohol having no OH group, water, or a mixture thereof are preferable.

In the cleaning method of the present invention, the water-repellent chemical solution, that is, the water-repellent chemical solution for a silicon-based wafer or the water-repellent chemical solution for a metal-based wafer is set to 40 ° C or higher. The solvent, which may be used for dilution in the chemical solution, . A solvent having a boiling point of less than 40 ° C may be used, but it is also possible to use another solvent having a boiling point of more than 40 ° C as a component (hereinafter referred to as a main solvent component) having the greatest mass ratio among components contained in the above water- And the like). The main solvent component preferably has a boiling point of 50 캜 or higher, and more preferably 70 캜 or higher.

The water-repellent chemical solution for silicon-based wafers may contain an additive or the like in addition to the silicon compound A, acid or base represented by the general formula [1], or a solvent. Likewise, the water-repellent chemical solution for a metal-based wafer may contain at least one kind of compound selected from the group consisting of the compounds represented by the general formulas [6] to [12] and salt compounds thereof, . Examples of the additive include hydrogen peroxide, an oxidizing agent such as ozone, and a surfactant. In the case where a part of the uneven pattern of the wafer contains a material in which the water repellent coating is not formed in the silicon compound A or the compound represented by the general formulas [6] to [12], a water repellent coating is formed on the material May be added. In the above water-repellent chemical solution for a silicon wafer, other acid may be added for the purpose of obtaining the silicon compound B.

In the present invention, the cleaning method of the wafer is not particularly limited as long as the water repellent liquid or the cleaning liquid can be held in at least the concave portion of the concavo-convex pattern of the wafer. Examples of the cleaning method of the wafer include a single cleaning method such as a spin cleaning method in which a wafer is cleaned one by one by supplying a liquid in the vicinity of the rotation center while rotating the wafer substantially horizontally, And a batch method in which a plurality of wafers are immersed and cleaned. The form of the water repellent liquid or the cleaning liquid when supplying the water repellent liquid or the cleaning liquid to at least the concave portion of the concavo-convex pattern of the wafer is not particularly limited as long as it becomes liquid when held in the concave portion. For example, Steam and so on.

In the present invention, the wafer is not particularly limited as long as it has a concavo-convex pattern. For example, a wafer containing a silicon element, a titanium, A wafer having at least one kind of element is used.

The wafer containing the silicon element on the surface of the concave portion of the concavo-convex pattern can be obtained, for example, by forming at least one component selected from silicon, silicon oxide and silicon nitride on at least the concave surface of the wafer, , At least the surface of the concave portion is made of at least one component selected from silicon, silicon oxide, and silicon nitride. When at least one component selected from silicon, silicon oxide, and silicon nitride is formed on at least a part of the concave surface of the wafer, or when at least a part of the concave surface is formed of silicon, silicon oxide , Silicon nitride, and silicon nitride. In this case, a water-repellent film is formed by at least one surface selected from silicon, silicon oxide, and silicon nitride present in at least a part of the concave surface by the water-repellent chemical solution for silicon wafer. Therefore, the water-repellent coating may be formed on at least a part of the concave surface of the wafer.

The wafer having at least one element selected from the group consisting of titanium, tungsten, aluminum, copper, tin, tantalum, and ruthenium on the surface of the concave portion of the concavo-convex pattern includes a silicon wafer, silicon and / or silicon oxide (SiO ₂ ) The surface of a wafer composed of a plurality of components, a silicon carbide wafer, a sapphire wafer, various compound semiconductor wafers, and a plastic wafer may be formed of a material containing a titanium element such as titanium, titanium nitride, or titanium oxide or a material containing a titanium element such as tungsten or tungsten oxide A material containing a tungsten element, a material containing an aluminum element such as aluminum or aluminum oxide, a material containing a copper element such as copper or copper oxide, a material containing a tin element such as tin or tin oxide, A material containing a tantalum element such as tantalum or a material containing a ruthenium element such as ruthenium or ruthenium oxide , Or a multilayered film is formed on a wafer, and at least one of the layers is a layer of a material containing the metal-based element. In the step of forming the concavo-convex pattern, In a layer comprising a layer of material. Also, at least a part of the surface of the concavo-convex pattern when the concavo-convex pattern is formed includes a material having at least one kind of element among the metal-based elements.

In addition, even for a wafer composed of a plurality of components including a substance having at least one element among the above-mentioned metal-based elements, the surface of a substance having at least one element of the metal- A coating film can be formed. As the wafer composed of the plurality of components, a material having at least one kind of element among the metal elements is formed at least on a part of the concave portion, or a part of the surface of at least the concave portion is formed of a metal- And at least one kind of element. What is able to form the water repellent coating with the water-repellent chemical for the metal-based wafer of the present invention is the surface of the material portion having at least one element among the metal-based elements in the uneven pattern. Therefore, the water-repellent film may be formed by a water-repellent chemical solution for a metal-based wafer on at least a part of the concave surface of the metal-based wafer.

Further, the cleaning method of the present invention is particularly preferably,

(Step 1) A step of providing a water-based liquid on the surface of the wafer with a surface having a concavo-convex pattern, holding the aqueous liquid in at least a concave portion of the concave-

(Step 2) A step of replacing the liquid held in at least the concave portion of the concavo-convex pattern with a cleaning liquid containing 80% by mass or more of a solvent having a boiling point of 55 to 200 캜,

(Step 3) The step of replacing the cleaning liquid with a water-repellent chemical liquid and holding the chemical liquid in at least concave portions of the uneven pattern,

(Step 4) A step of removing liquid from the surface of the concavo-convex pattern by drying,

(Step 5) Step of removing water repellent film

Respectively.

First, as described in the above (Step 1), the water-based liquid is held in at least the concave portion of the concavo-convex pattern. Examples of the acid which may be mixed with the aqueous liquid include an inorganic acid and an organic acid. Examples of the inorganic acid include hydrofluoric acid, buffered hydrofluoric acid, sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid. Examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid, And propionic acid. Examples of the alkali which may be mixed in the cleaning liquid include ammonia and choline. Examples of the oxidizing agent which may be mixed in the cleaning liquid include ozone and hydrogen peroxide.

Next, as described in the above (Step 2), the liquid held in the concave portion is replaced with a cleaning liquid containing 80% by mass or more of a solvent having a boiling point of 55 to 200 캜. Further, the liquid held in the concave portion before the replacement may be the above-described aqueous liquid or may be the rinse liquid A described later.

It is preferable that the cleaning liquid is at least one liquid selected from the group consisting of an organic solvent, water, and an aqueous solution in which at least one of an organic solvent, an acid, an alkali, and an oxidizer is mixed with water.

In the case of preparing the cleaning liquid containing an organic solvent having a boiling point of less than 55 캜, an organic solvent having a boiling point of less than 55 캜 and water or an organic solvent having a boiling point of 55 to 200 캜 are mixed, The cleaning liquid is prepared so as to contain at least 80 mass% of the solvent at 55 to 200 deg. In the case of preparing the cleaning liquid containing an organic solvent having a boiling point higher than 200 ° C, an organic solvent having a boiling point of higher than 200 ° C and water or an organic solvent having a boiling point of 55 to 200 ° C are mixed, The cleaning liquid is prepared so as to contain at least 80% by mass of a solvent having a boiling point of 55 to 200 ° C.

The cleaning liquid is preferably an organic solvent, water, or a mixture of water and an organic solvent from the viewpoint of cleanliness. Further, if the cleaning liquid is an organic solvent, the water repellent liquid can be provided in the concave portion without contacting with water, which is preferable. Particularly, when the organic solvent contains a water-soluble organic solvent (the solubility to 100 parts by mass of water is not less than 5 parts by mass), it is preferable to easily replace it from the aqueous liquid.

Further, after the step (step 1) of holding the aqueous liquid in the concave portion, the aqueous liquid held in at least the concave portion of the concave-convex pattern may be referred to as a liquid different from the liquid (hereinafter referred to as the rinse liquid A (Step 2) in which the cleaning liquid is replaced with the cleaning liquid.

As the rinsing liquid A, a plurality of liquids may be used in place of the liquid. For example, it can be used as a rinse liquid A after substitution with water and further substituting with an organic solvent (preferably a water-soluble organic solvent).

Next, as described in (Step 3), the water-repellent chemical is held in at least the concave portion of the concavo-convex pattern, and the water-repellent film is formed on the concave surface of the concavo-convex pattern of the wafer by the water- The temperature of the water-repellent chemical solution provided in the replacing step is 40 占 폚 or higher and lower than the boiling point of the water-repellent chemical solution.

When the water-repellent film is formed by the water-repellent chemical on the concave surface of the concavo-convex pattern of the wafer, the contact angle when it is assumed that water is retained on the surface is preferably from 50 to 130 DEG because pattern collapse hardly occurs . Further, the closer the contact angle is to 90 deg., The smaller the capillary force acting on the concave portion becomes, and the more the pattern collapse becomes difficult to occur, the more preferable is 60 to 120 deg., And the more preferable it is 70 to 110 deg. The capillary force is preferably 2.1 MN / m 2 or less. If the capillary force is 2.1 MN / m < 2 > or less, pattern collapse is unlikely to occur, which is preferable. Further, when the capillary force becomes smaller, pattern collapse becomes more difficult to occur. Therefore, the capillary force is particularly preferably 1.5 MN / m 2 or less, and more preferably 1.0 MN / m 2 or less. It is also ideal to adjust the contact angle with the liquid to about 90 degrees to approach the capillary force endlessly to 0.0MN / m < 2 >.

Next, as described in (Step 4), a step of removing the liquid from the surface of the concavo-convex pattern by drying is performed. In this process, the liquid retained on the surface of the relief pattern is removed by drying. The drying is preferably carried out by a well-known drying method such as spin drying, IPA (2-propanol) steam drying, Marangoni drying, heat drying, air drying, hot air drying and vacuum drying.

Further, after the step (step 3) of holding the water-repellent chemical liquid at least on the concave portion of the concavo-convex pattern, the water-repellent chemical liquid held in at least the concave portion of the concave- (Step 4) in which the liquid is removed from the surface of the concavo-convex pattern by drying.

As the rinsing liquid B, a plurality of cleaning liquids may be substituted. For example, the rinse liquid B may be replaced with an organic solvent (preferably a water-soluble organic solvent) and then an aqueous liquid.

Examples of the rinsing liquid A and the rinsing liquid B include water, an organic solvent, a mixture of water and an organic solvent, a mixture of at least one of an acid, an alkali and a surfactant, or a mixture thereof with the water- At least one compound selected from the group consisting of the silicon compound A, the silicon compound A and the acid or base, and the compound represented by the general formula [6] to [12] and the salt compound thereof is contained in the water- And those added so as to have a lower concentration.

Examples of the organic solvent which is one of preferable examples of the cleaning liquid, rinse liquid A and rinse liquid B include hydrocarbons, esters, ethers, ketones, halogen element-containing solvents, sulfoxide-based solvents, alcohols, derivatives of polyhydric alcohols , A nitrogen element-containing solvent, and the like.

Specific examples of the organic solvent include the same organic solvents that may be used for dilution in the water-repellent chemical solution for silicon-based wafers and organic solvents used for the water-repellent chemical solution for metal wafers.

When the liquid is removed from the surface of the concavo-convex pattern, the liquid retained on the surface may be the water repellent liquid, the rinse liquid B, and a mixture thereof. The mixed solution containing the water-repellent chemical may be a solution in the middle of replacing the water-repellent chemical with the rinse solution B, or may be a mixed solution obtained by mixing the water-repellent chemical solution with a rinse solution B different from the water- . Alternatively, after the liquid is once removed from the surface of the concave-convex pattern, the rinse liquid B or the mixed liquid may be held on the surface of the concave-convex pattern, and then dried. When the liquid is removed from the surface of the concave-convex pattern, the water-repellent coating is present on the surface of the concave portion, so that the capillary force applied to the concave portion is reduced, and pattern collapse hardly occurs.

In the step (step 4) of removing the liquid from the surface of the concavo-convex pattern by drying, the liquid removed from the surface of the concavo-convex pattern is water, the organic solvent, or a mixture thereof in the rinsing liquid B, So that dirt is hardly left on the surface. Further, in the case of a water-based liquid, particularly water, the contact angle? Of the surface of the concave portion of the concavo-convex pattern which is water-repellent by the water-repellent chemical solution becomes large and the capillary force P acting on the concave portion becomes small.

Also, the cleaning liquid, rinse liquid A, and rinse liquid B may be maintained at a temperature of 10 占 폚 or higher and lower than the boiling point of the liquid. For example, as the rinsing liquid A, a solution containing an acidic aqueous solution, particularly preferably a solution containing an acidic aqueous solution and an organic solvent having a boiling point of 100 ° C or higher, is used to adjust the temperature of the rinsing liquid A to the vicinity of the boiling point of the rinsing liquid A , It is preferable that the water-repellent film is easily formed in a short time.

Next, as described in (Step 5), a step of removing the water-repellent film is performed. In the case of removing the water-repellent film, it is effective to cut the C-C bond and the C-F bond in the water-repellent film. The method is not particularly limited as long as it is capable of cutting the bond. For example, the wafer is irradiated with light, the wafer is heated, the wafer is exposed to ozone, the wafer is irradiated with plasma, And corona discharge on the surface.

When the water-repellent film is removed by light irradiation, 340 nm, which is an energy equivalent to 83 ㎉ / mol, 116 ㎉ / mol, which is the binding energy of CC bond and CF bond in the water-repellent film, . As the 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. The ultraviolet ray irradiation intensity was measured with a light intensity meter UM-10 manufactured by Konica Minolta Sensing, Inc., a light receiving part UM-360 (peak sensitivity wavelength: 365 nm, measurement wavelength range: 310 to 400 nm)] is preferably at least 100 mW / cm 2, more preferably at least 200 mW / cm 2. When the irradiation intensity is less than 100 mW / cm < 2 >, it takes a long time to remove the water-repellent film. If the low-pressure mercury lamp is irradiated with ultraviolet rays having a shorter wavelength, the water repellent film can be removed in a short time even if the irradiation intensity is low.

Further, when the water-repellent film is removed by light irradiation, the components of the water-repellent film are decomposed with ultraviolet rays, and ozone is generated. When the components of the water-repellent film are oxidized and volatilized by the ozone, the processing time is shortened Particularly preferred. As this light source, a low-pressure mercury lamp or an excimer lamp is used. Further, the wafer may be heated while irradiating light.

When the wafer is heated, the wafer is heated at 400 to 700 占 폚, preferably 500 to 700 占 폚. The heating time is preferably 0.5 to 60 minutes, preferably 1 to 30 minutes. In this process, ozone exposure, plasma irradiation, corona discharge, or the like may be used in combination. Alternatively, light irradiation may be performed while heating the wafer.

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

In the step of removing the water repellent film on the wafer surface, the water repellent film on the wafer surface can be efficiently removed by combining the light irradiation, heating, ozone exposure, plasma irradiation, corona discharge, and the like.

Example

Since the surface of the wafer is made of a surface having a concavo-convex pattern, various studies have been made in other documents and the like, and since it is an established technique, in the present invention, the evaluation of the surface treatment of the wafer using the water- In addition,

P = 2 x? X cos? / S

(Where? Is the surface tension of the liquid held in the concave portion,? Is the contact angle between the concave portion surface and the liquid held in the concave portion, and S is the width of the concave portion) The contact angle of the held liquid to the wafer surface, that is, the contact angle of the liquid droplet of the liquid, and the surface tension of the liquid. In the case of the liquid held in the concave portion 4 of the concavo-convex pattern 2, the contact angle of the liquid droplet and the capillary force acting on the concave portion, which may be considered equivalent to the pattern collapse, Therefore, the capillary force may be derived from the above formula and the evaluation of the contact angle of the droplet of the water-repellent coating film 12. In the examples, water, which is a typical example of an aqueous liquid, was used as the liquid.

However, in the case of a wafer having a concavo-convex pattern on its surface, the contact angle of the water-repellent coat 12 itself formed on the concavo-convex pattern surface can not be accurately evaluated.

The evaluation of the contact angle of water droplets is carried out by dropping a few μL of water on the surface of a sample (base material) as described in JIS R 3257 "Wettability Test Method of Substrate Glass Surface" Is measured by measuring the angle formed. However, in the case of a wafer having a pattern, the contact angle becomes very large. This is because the Wenzel effect or the Cassie effect is generated, and the contact angle affects the surface shape (roughness) of the substrate, thereby increasing the contact angle of the apparent numerical value.

Thus, in this embodiment, the water-repellent liquid is provided on a wafer having a smooth surface, and a water-repellent film is formed on the surface of the wafer to form a water-repellent film on the surface of the wafer 1, It was regarded as the coating film 12, and various evaluations were carried out. In this embodiment, a silicon wafer having a smooth surface, a "wafer having a thermally oxidized film" having a smooth thermal oxide film layer on a silicon wafer having a smooth surface, a smooth silicon wafer having a smooth surface, Quot; wafer having a silicon nitride film " In addition, as a metal-based wafer having a smooth surface, a "wafer having a titanium nitride film" having a titanium nitride layer on a silicon wafer having a smooth surface, a wafer having a "tungsten film having a tungsten layer on a smooth silicon wafer" And a " wafer having a ruthenium film " having a ruthenium layer on a silicon wafer having a smooth surface.

In the cleaning method of providing the liquid to the wafer while rotating the wafer, it is very difficult to strictly reproduce the state of substitution from the cleaning liquid to the water-repellent chemical. Therefore, in this embodiment, the wafer immersed in the cleaning liquid is removed The immersed state in the water-repellent chemical solution in the state in which the cleaning liquid was maintained was reproduced with good precision. In addition, the water-repellent state of the wafer (the state of the water-repellent film) was evaluated by varying the immersion time in the water-repellent chemical solution, when the progress of the substitution was changed.

Details are described below. Hereinafter, the evaluation method of the wafer provided with the water-repellent chemical solution, the preparation of the water-repellent chemical solution, and the evaluation result after providing the water-repellent chemical solution on the wafer are described.

[Evaluation method of wafers provided with water-repellent chemical solution]

(1) to (2) as evaluation methods of wafers provided with water-repellent chemical solutions.

(1) Evaluation of contact angle of water-repellent film formed on wafer surface

About 2 μl of pure water was placed on the surface of the wafer having the water-repellent coating, and the angle (contact angle) between the water surface and the wafer surface was measured with a contact angle meter (CA-X: Kyowa Interface Science Co., Type). This measurement was performed at five points on the wafer surface, and an average value was calculated.

(2) Evaluation of capillary force

P was calculated using the following formula, and the capillary force (absolute value of P) was obtained.

P = 2 x? X cos? / S

(Where? Is the surface tension of the liquid held in the recess,? Is the contact angle between the surface of the recess and the liquid held in the recess, and S is the width of the recess).

In this embodiment, as an example of a pattern shape, a wafer having a line-and-space pattern with a line width (width of a recess) of 45 nm is assumed. In the case of a pattern having a concave portion width of 45 nm, the pattern tends to collapse when the cleaning liquid when the gas-liquid interface passes through the concavo-convex pattern is water, and the pattern tends to be hardly collapsed when it is 2-propanol. When the width of the concave portion is 45 nm and the surface of the wafer is silicon oxide, the capillary force becomes 0.98 MN / m 2 when the cleaning liquid is 2-propanol (surface tension: 22 mN / m, contact angle with respect to the silicon oxide surface: 1 °). On the other hand, the capillary force is 3.2 MN / m 2 in the case of water having the greatest surface tension (surface tension: 72 mN / m, contact angle with silicon oxide: 2.5 °) in the liquid other than mercury. When the surface of the wafer is, for example, titanium nitride, tungsten or ruthenium, the contact angles of 2-propanol with respect to the surface are all 0.5 °, and the contact angles of water are all 2 °. The same is true for materials containing other titanium atoms, tungsten atoms or ruthenium elements (for example, titanium, titanium oxide, tungsten oxide, ruthenium oxide, etc.). In the case of a wafer having a titanium nitride film or a wafer having a tungsten film and a ruthenium film having a concave portion having a width of 45 nm, the capillary force is 0.98 MN / m 2 in 2-propanol (surface tension: 22 mN / m) . On the other hand, the capillary force is 3.2 MN / m 2 in the surface tension (surface tension: 72 mN / m) of liquid other than mercury.

[Example 1-1]

(1) Cleaning of wafers by cleaning liquid

(A silicon wafer having a thermally oxidized film layer having a thickness of 1 占 퐉 on the surface) having a smooth thermal oxide film was immersed in a 1% by mass hydrofluoric acid aqueous solution at room temperature for 2 minutes, followed by 1 minute in pure water, 2-propanol ; Boiling point 82 占 폚) for 1 minute. Therefore, the cleaning liquid retained on the surface of the wafer after cleaning is iPA.

(2) Preparation of water-repellent chemical solution

In this example, 5 g of hexamethyldisilazane [(H ₃ C) ₃ Si-NH-Si (CH ₃ ) ₃ ] as the silicon compound A and 5 g of trimethylsilyltrifluoroacetate [(CH ₃ ) ₃ Si-OC (O) CF ₃ ] and 94.9 g of propylene glycol monomethyl ether acetate (PGMEA) as an organic solvent were mixed to obtain a water-repellent chemical solution. Among the components contained in the water-repellent chemical solution, the component having the largest amount by mass ratio is PGMEA, and its boiling point is 146 占 폚.

(3) Replacement of the cleaning liquid on the wafer surface by the water repellent chemical liquid

The water-repellent chemical solution prepared in (2) preparation of the water-repellent chemical solution was heated to 40 ° C and the wafer having the thermally oxidized film prepared in the above (1) cleaning of the wafer was immersed in the chemical solution for 5, 10, 20, 30, 40, 50, 60 sec), and the cleaning liquid was replaced to form a water repellent coating film. Thereafter, the wafer having the thermally oxidized film was pulled up from the solution, immersed in iPA for 60 seconds as a rinse solution, and then immersed in pure water for 60 seconds.

(4) Drying of wafers

Finally, the wafer having the thermal oxide film was taken out from the pure water, blown air was blown and dried to remove pure water from the surface.

The obtained wafer having the thermally oxidized film was evaluated by the method described in the above-mentioned "evaluation method of the wafer provided with the water-repellent chemical solution", and the contact angle of the wafer having the thermally oxidized film after the surface treatment was 75 ° or more, 80 ° or more, (I.e., a capillary force of 0.8 MN / m 2 or less, 0.6 MN / m 2 or less, and 0.3 MN / m 2 or less, respectively). The results are shown in Table 1.

[Examples 1-2 to 1-10, Comparative Examples 1-1 to 1-5]

The temperature of the water-repellent chemical used in Example 1-1, the cleaning liquid before the water-repelling treatment, and the solvent of the water-repellent chemical solution were changed to perform the surface treatment of the wafer having the thermal oxidation film. The results are shown in Table 1. Further, DEGEEA means diethylene glycol monoethyl ether acetate. Of the components contained in the water-repellent chemical solution using the solvent, the component having the greatest mass ratio is DEGEEA, and its boiling point is 218 ° C. Also, PGDA means propylene glycol diacetate, and among the components contained in the water-repellent chemical solution using the solvent, the component having the largest amount by mass ratio is PGDA, and its boiling point is 190 占 폚. PGMEA / DEE means a solvent in which PGMEA and diethyl ether (DEE; boiling point: 35 ° C) are mixed at a mass ratio of 90:10. Among the components contained in the water-repellent chemical solution using the mixed solvent, PGMEA / Many components are PGMEA, and its boiling point is 146 占 폚. Likewise, PGMEA / DEGEEA means a solvent in which PGMEA and DEGEEA are mixed in a mass ratio of 90:10. Among the components contained in the water-repellent chemical solution using the mixed solvent, PGMEA is the component having the greatest mass ratio, 146 ° C. Similarly, DEGEEA / PGMEA means a solvent in which DEGEEA and PGMEA are mixed in a mass ratio of 90:10. Of the components contained in the cleaning solvent using the mixed solvent, the component having the greatest mass ratio is DEGEEA, and its boiling point is 218 / RTI >

[Example 2-1]

5 g of hexamethyldisilazane [(H ₃ C) ₃ Si-NH-Si (CH ₃ ) ₃ ] as the silicon compound D and 5 g of trifluoroacetic anhydride [{CF ₃ C (O)} ₂ O And 94.9 g of PGMEA as an organic solvent were mixed and reacted to prepare a water repellent chemical solution containing trimethylsilyl trifluoroacetate as a silicon compound B, hexamethyldisilazane as a silicon compound A, and PGMEA as an organic solvent The procedure of Example 1-1 was otherwise followed. Among the components contained in the water-repellent chemical solution, the component having the largest amount by mass ratio is PGMEA, and its boiling point is 146 占 폚. The hexamethyldisilazane contained in the water-repellent chemical solution of this example is a silicon compound D which was not consumed in the reaction for obtaining the silicon compound B, and the component functions as the silicon compound A. The results are shown in Table 2.

[Examples 2-2 to 2-6, Comparative Examples 2-1 to 2-4]

The temperature of the water-repellent chemical used in Example 2-1, the cleaning liquid before the water-repelling treatment, and the solvent of the water-repellent chemical solution were changed to perform the surface treatment of the wafer having the thermally oxidized film. The results are shown in Table 2.

[Example 3-1]

The procedure of Example 2-1 was repeated except that the acid D was changed to trifluoroacetic acid [CF ₃ C (O) -OH]. Of the components contained in the water-repellent chemical solution obtained in this Example, the component having the largest amount by mass ratio is PGMEA, and its boiling point is 146 占 폚. The results are shown in Table 3.

[Examples 3-2 to 3-6, Comparative Examples 3-1 to 3-4]

The temperature of the water-repellent chemical solution used in Example 3-1, the cleaning liquid before the water-repellent treatment, and the solvent of the water-repellent chemical solution were changed to perform the surface treatment of the wafer having the thermal oxide film. The results are shown in Table 3.

[Example 4-1]

Except that trimethylsilyldimethylamine [(CH ₃ ) ₃ Si-N (CH ₃ ) ₂ ] was used as silicon compound A and silicon compound B was not used. Of the components contained in the water-repellent chemical solution obtained in this Example, the component having the largest amount by mass ratio is PGMEA, and its boiling point is 146 占 폚. The results are shown in Table 4.

[Examples 4-2 to 4-4, Comparative Examples 4-1 to 4-2]

The temperature of the water-repellent chemical solution used in Example 4-1 and the cleaning liquid before the water-repellent treatment were changed to perform the surface treatment of the wafer having the thermal oxidation film, and the evaluation was carried out. The results are shown in Table 4.

[Example 5-1]

The procedure of Example 4-1 was repeated except that octyldimethyl (dimethylamino) silane [C ₈ H ₁₇ Si (CH ₃ ) ₂ -N (CH ₃ ) ₂ ] was used as the silicon compound A. Of the components contained in the water-repellent chemical solution obtained in this Example, the component having the largest amount by mass ratio is PGMEA, and its boiling point is 146 占 폚. The results are shown in Table 5.

[Examples 5-2 to 5-7, Comparative Examples 5-1 to 5-2]

The temperature of the water-repellent chemical used in Example 5-1, the cleaning liquid before the water-repelling treatment, and the solvent of the water-repellent chemical solution were changed to perform the surface treatment of the wafer having the thermal oxide film. The results are shown in Table 5. DPGMEA means dipropylene glycol monomethyl ether acetate (boiling point: 213 DEG C), and 13BGDA means 1,3-butylene glycol diacetate (boiling point: 232 DEG C).

[Example 6-1]

(1) Cleaning of wafers by cleaning liquid

A silicon wafer having a smooth silicon nitride film (a silicon wafer having a silicon nitride layer having a thickness of 50 nm on the surface) was immersed in a 1% by mass aqueous solution of hydrofluoric acid for 2 minutes at room temperature. Subsequently, the wafer was immersed in pure water for 1 minute and 28% Was immersed in a mixed solution of 30 mass% hydrogen peroxide and water at a ratio of 1: 1: 5 (volume ratio) at 70 DEG C for 1 minute, at room temperature for 1 minute, for iPA for 1 minute, and for PGMEA (boiling point: 146 DEG C) . Therefore, the cleaning liquid retained on the wafer surface after cleaning is PGMEA.

(2) Preparation of water-repellent chemical solution

5 g of octyldimethyl (dimethylamino) silane [C ₈ H ₁₇ Si (CH ₃ ) ₂ -N (CH ₃ ) ₂ ] as the silicon compound D, and trifluoroacetic anhydride [{CF ₃ C } ₂ O) and 94.8 g of PGMEA as an organic solvent were mixed and reacted to prepare octyldimethylsilyl trifluoroacetate as the silicon compound B, octyldimethyl (dimethylamino) silane as the silicon compound A, and PGMEA To obtain a water-repellent chemical solution. Among the components contained in the water-repellent chemical solution, the component having the largest amount by mass ratio is PGMEA, and its boiling point is 146 占 폚.

In the same manner as in Example 1-2, the surface of the wafer having the silicon nitride film was treated with a water-repellent chemical solution and evaluated. The results are shown in Table 6.

[Examples 6-2 to 6-6, Comparative Examples 6-1 to 6-2]

The surface of the wafer having the silicon nitride film was subjected to the surface treatment by changing the temperature of the water-repellent chemical solution used in Example 6-1, the cleaning liquid before the water-repellent treatment and the solvent of the water-repellent chemical solution. The results are shown in Table 6. Further, PGMEA / GBL means a mixed solvent of PGMEA: gamma -butyrolactone = 60: 40 (mass ratio). Of the components contained in the water-repellent chemical solution using the mixed solvent, the component having the largest amount by mass ratio is PGMEA, and its boiling point is 146 占 폚.

[Example 7-1]

(1) Cleaning of wafers by cleaning liquid

A wafer (a silicon wafer having a titanium nitride layer having a thickness of 50 nm on the surface) having a smooth titanium nitride film was immersed in a 1% by mass aqueous hydrogen peroxide solution at room temperature for 1 minute and then at room temperature, pure water for 1 minute, PGMEA (boiling point; 146 < 0 > C) for 1 minute. Therefore, the cleaning liquid retained on the wafer surface after cleaning is PGMEA.

(2) Preparation of water-repellent chemical solution

0.01 g of perfluorohexylethylphosphonic acid [C ₆ F ₁₃ -C ₂ H ₄ -P (O) (OH) ₂ ] and 99.999 g of a mixed solvent of PGMEA: iPA = 99.89: Were mixed and stirred (stirred) for 18 hours to obtain a water-repellent chemical solution. Among the components contained in the water-repellent chemical solution, the component having the largest amount by mass ratio is PGMEA, and its boiling point is 146 占 폚.

In the same manner as in Example 1-2, the surface of the wafer having the titanium nitride film was treated with a water-repellent chemical solution and evaluated. The results are shown in Table 7.

[Examples 7-2 to 7-5 and Comparative Examples 7-1 to 7-2]

The surface of the wafer having the titanium nitride film was subjected to the surface treatment by changing the temperature of the water-repellent chemical solution used in Example 7-1, the cleaning liquid before the water-repelling treatment, and the solvent of the water-repellent chemical solution. The results are shown in Table 7. Further, DEGEEA / iPA means a mixed solvent of DEGEEA: iPA = 99.89: 0.1 (mass ratio). Of the components contained in the water-repellent chemical solution using the mixed solvent, the component having the greatest mass ratio is DEGEEA, Lt; / RTI > PGDA / iPA means a mixed solvent of PGDA: iPA = 99.89: 0.1 (mass ratio). Of the components contained in the water-repellent chemical solution using the mixed solvent, PGDA / iPA is PGDA in its mass ratio, Lt; / RTI > DPGMEA / iPA means a mixed solvent of DPGMEA: iPA = 99.89: 0.1 (by mass ratio). Of the components contained in the water-repellent chemical solution using the mixed solvent, DPGMEA is the component having the highest mass ratio, Lt; / RTI > 13BGDA / iPA means a mixed solvent of 13BGDA: iPA = 99.89: 0.1 (mass ratio). Of the components contained in the water-repellent chemical solution using the mixed solvent, the component having the greatest mass ratio is 13BGDA, 232 ° C.

[Example 8-1]

Octyl acid _{[C 8 H 17 -P (O)} (OH) 2 ]; and 0.01g, PGMEA as a solvent: iPA = 99.89: 0.1 (mass ratio) mixed solvent of; a mixture of 99.99g and stirred for 18 hours the water repellent The same procedure as in Example 7-1 was carried out except that a chemical solution was obtained. Of the components contained in the water-repellent chemical solution obtained in this Example, the component having the largest amount by mass ratio is PGMEA, and its boiling point is 146 占 폚. The results are shown in Table 8.

[Examples 8-2 to 8-4, Comparative Examples 8-1 to 8-2]

The surface of the wafer having the titanium nitride film was subjected to the surface treatment by changing the temperature of the water-repellent chemical solution used in Example 8-1, the cleaning liquid before the water-repelling treatment, and the solvent of the water-repellent chemical solution. The results are shown in Table 8.

[Example 9-1]

(A silicon wafer having a tungsten layer having a thickness of 50 nm on the surface) having a smooth tungsten film on the wafer, immersing it in ammonia water of 5% by mass at room temperature for 1 minute and then for 1 minute at room temperature, (Boiling point: 146 占 폚) for 1 minute, and then subjected to surface treatment. Therefore, the cleaning liquid retained on the wafer surface after cleaning is PGMEA. The results are shown in Table 9.

[Examples 9-2 to 9-4, Comparative Examples 9-1 to 9-3]

The surface of the wafer having the tungsten film was subjected to the surface treatment by changing the temperature of the water-repellent chemical solution used in Example 9-1, the cleaning liquid before the water-repelling treatment, and the solvent of the water-repellent chemical solution. The results are shown in Table 9.

[Example 10-1]

The wafer was immersed in 5% by mass ammonia water at room temperature for 1 minute using a wafer having a smooth ruthenium film (a silicon wafer having a ruthenium layer having a thickness of 300 nm on the surface), and then immersed in pure water for 1 minute, PGMEA ( (Boiling point: 146 占 폚) for 1 minute, and then subjected to surface treatment. Therefore, the cleaning liquid retained on the wafer surface after cleaning is PGMEA. The results are shown in Table 10.

[Examples 10-2 to 10-5 and Comparative Examples 10-1 to 10-3]

The surface of the wafer having the ruthenium film was subjected to the surface treatment by changing the temperature of the water-repellent chemical used in Example 10-1, the cleaning liquid before the water-repellent treatment, and the solvent of the water-repellent chemical. The results are shown in Table 10.

In this embodiment, the boiling point of the washing liquid before the water-repellent treatment is set to 55 to 200 ° C, and the temperature of the water-repellent chemical is set to 40 ° C or higher and less than the boiling point of the water-repellent chemical. In this embodiment, . On the other hand, it was confirmed that the comparative example requires time to impart water repellency. Therefore, even when the temperature of the chemical solution is raised to promote the formation of the water-repellent film by performing annealing after the replacement of the cleaning solution with the chemical solution from the cleaning solution, the time required for the replacement is long and an additional time is required , Water repellency can not be imparted in a short period of time as in the examples. In addition, among the examples, it was confirmed that water repellency can be imparted in a shorter time by increasing the temperature of the water-repellent chemical.

1: Wafer 2: Uneven pattern of the wafer surface
3: convex part of pattern 4: concave part of pattern
5: width of concave portion 6: height of convex portion
7: width of convex portion 8: cleaning liquid
9: Water repellent solution
10: Mixing of washing liquid and water repellent liquid
11: the cleaning liquid evaporates 12: the water repellent coating

Claims (12)

A cleaning method for a wafer having a concavo-convex pattern on its surface,
A step of cleaning the wafer with a cleaning liquid,
A step of replacing the cleaning liquid held in the concave portion of the wafer with the water repellent chemical after cleaning,
And a step of drying the wafer,
The cleaning liquid contains 80% by mass or more of a solvent having a boiling point of 55 to 200 캜,
The temperature of the water-repellent chemical liquid provided in the replacing step is set to 40 DEG C or higher and less than the boiling point of the water-repellent chemical liquid,
The water-repellent chemical solution may be any one of a hydrocarbon, an ester, an ether, a ketone, a halogen-containing solvent, a sulfoxide-based solvent, a lactone-based solvent, a carbonate-based solvent or a derivative of a polyhydric alcohol, Containing solvent, or a mixture thereof,
Wherein the wafer is a wafer containing a silicon element on the surface of the recess, and the water repellent chemical contains a silicon compound A represented by the following general formula [1], or a silicon compound A containing an acid or base And cleaning the wafer.
(R ¹ ) _a Si (H) _b X ¹ _4-ab [1]
[In the formula [1], R ¹ is a monovalent organic group including monovalent hydrocarbon groups of 1 to 18 carbon atoms, in which some or all of hydrogen atoms may be substituted with fluorine atoms. X ¹ represents a monovalent functional group in which the element bonding to the silicon element is nitrogen, a monovalent functional group in which the element bonding to the silicon element is oxygen, a halogen group, a nitrile group, and -CO-NH-Si ( CH ₃ ) ₃ . a is an integer of 1 to 3, b is an integer of 0 to 2, and the sum of a and b is 1 to 3.] The method according to claim 1,
Wherein the cleaning liquid is at least one liquid selected from the group consisting of an organic solvent, water, and an aqueous solution in which at least one of an organic solvent, an acid, an alkali, and an oxidizer is mixed with water. The method according to claim 1,
Wherein the water repellent liquid comprises an acid, and the acid is selected from the group consisting of hydrogen chloride, sulfuric acid, perchloric acid, phosphoric acid, a sulfonic acid and an anhydride thereof represented by the following general formula [2], a carboxylic acid and an anhydride thereof represented by the general formula [ At least one compound selected from the group consisting of alkyl borate ester, aryl borate ester, tris (trifluoroacetoxy) boron, trialkoxyboroxine, trifluoroboron, and silicon compound B represented by the following general formula [4] And cleaning the wafer.
R ² S (O) ₂ OH [2]
[In the formula [2], R ² is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms.]
R ³ COOH [3]
[In the formula [3], R ³ is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with a fluorine atom.]
(R ⁴ ) _c Si (H) _d X ² _4-cd [4]
[In the formula [4], R ⁴ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be substituted with fluorine atoms in part or all of hydrogen atoms. X ² is, independently of each other, a chloro group, -OCO-R ⁵ (R ⁵ is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms), and -OS (O) _2- R ⁶ (R ⁶ represents at least one group selected from the group consisting of a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms). c is an integer of 1 to 3, d is an integer of 0 to 2, and the sum of c and d is 1 to 3.] The method according to claim 1,
The acid is preferably selected from the group consisting of trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyltrifluoroacetate, butyldimethylsilyltrifluoromethane Hexyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate, decyldimethylsilyl chloride, decyldimethylsilyltrifluoroacetate, decyldimethylsilyltrifluoroacetate, hexyldimethylsilyltrifluoromethanesulfonate, Wherein the cleaning liquid is at least one selected from the group consisting of trifluoromethanesulfonate, dodecyldimethylsilyl trifluoroacetate, and dodecyldimethylsilyltrifluoromethanesulfonate. The method according to claim 1,
The silicon compound A is at least one member selected from the group consisting of hexamethyldisilazane, trimethylsilyldimethylamine, trimethylsilyldiethylamine, tetramethyldisilazane, dimethylsilyldimethylamine, dimethylsilyldiethylamine, 1,3-dibutyltetramethyldisilane Butyldimethylsilyldimethylamine, butyldimethylsilyldimethylamine, butyldimethylsilyldiethylamine, 1,3-dihexyltetramethyldisilazane, hexyldimethylsilyldimethylamine, hexyldimethylsilyldiethylamine, 1,3-dioctyltetramethyldisilane But are not limited to, hexyldimethylsilyldimethylamine, octyldimethylsilyldimethylamine, octyldimethylsilyldiethylamine, 1,3-didecyltetramethyldisilazane, decyldimethylsilyldimethylamine, decyldimethylsilyldiethylamine, 1,3-didodecyltetramethyldisilane And at least one selected from the group consisting of dodecyldimethylsilyldimethylamine, dodecyldimethylsilyldiethylamine, and the like. The method according to claim 1,
Wherein the water repellent agent comprises a base and the base is selected from the group consisting of ammonia, N, N, N ', N'-tetramethylethylenediamine, triethylenediamine, dimethylaniline, alkylamine, dialkylamine, trialkylamine, Wherein the silicon compound C is at least one selected from the group consisting of piperazine, N-alkylmorpholine, and silicon compound C represented by the following general formula [5].
(R ⁷ ) _e Si (H) _f X ³ _4-ef [5]
[In the formula [5], R < ⁷ > is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms. X ³ is a monovalent functional group that is independent of each other and an element which bonds with the silicon element is nitrogen and may contain a fluorine atom or a silicon element. e is an integer of 1 to 3, f is an integer of 0 to 2, and the sum of e and f is 1 to 3.] 3. The method according to claim 1 or 2,
Wherein the temperature of the water-repellent chemical solution provided in the replacing step is 70 占 폚 or higher and the boiling point of the water-repellent chemical solution is lower than -10 占 폚. A silicon compound A represented by the following general formula [1]
A solvent containing no OH group and a solvent containing a nitrogen element having no NH group among derivatives of hydrocarbons, esters, ethers, ketones, halogen element-containing solvents, sulfoxide-based solvents, lactone-based solvents, carbonate-based solvents and polyhydric alcohols An organic solvent selected from the group consisting of an organic solvent and a mixture thereof,
(R ¹ ) _a Si (H) _b X ¹ _4-ab [1]
[In the formula [1], R ¹ is a monovalent organic group including monovalent hydrocarbon groups of 1 to 18 carbon atoms, in which some or all of hydrogen atoms may be substituted with fluorine atoms. X ¹ represents a monovalent functional group in which the element bonding to the silicon element is nitrogen, a monovalent functional group in which the element bonding to the silicon element is oxygen, a halogen group, a nitrile group, and -CO-NH-Si ( CH ₃ ) ₃ . a is an integer of 1 to 3, b is an integer of 0 to 2, and the sum of a and b is 1 to 3.]
Wherein the hydrocarbons are selected from the group consisting of toluene, benzene, xylene, hexane, heptane and octane, and the esters are selected from the group consisting of ethyl acetate, propyl acetate, butyl acetate and ethyl acetoacetate, Ethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran and dioxane, and the ketones are selected from the group consisting of acetone, acetyl acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone and isophorone And the halogen element-containing solvent is selected from the group consisting of perfluorocarbon, hydrofluorocarbon, hydrofluoroether, chlorocarbon, hydrochlorocarbon, chlorofluorocarbon, hydrochlorofluorocarbon, perfluoroether And perfluoropolyethers And the lactone-based solvent is selected from the group consisting of? -Butyrolactone,? -Valerolactone,? -Hexanolactone,? -Heptanolactone,? -Octanolactone, ? -undecanolactone,? -decanolactone,? -decanolactone,? -valanolactone,? -hexanolactone,? -octanolactone,? -nonanolactone, Wherein the carbonate solvent is selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and propylene carbonate, and the carbonate solvent is selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and propylene carbonate And those having no OH group among derivatives of the polyhydric alcohol are selected from the group consisting of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetic acid Ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol diethyl ether, Glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol Triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, Tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, Propylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol moiety Butyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol mono Butyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate and Glycerin triacetate, and the nitrogen element-containing solvent having no NH group is selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- Butyl amine, and the water repellent chemical is selected from the group consisting of pyridine. A cleaning method for a wafer having a concavo-convex pattern on its surface,
A step of cleaning the wafer with a cleaning liquid,
A step of replacing the cleaning liquid held in the concave portion of the wafer with the water repellent chemical after cleaning,
And a step of drying the wafer,
The cleaning liquid contains 80% by mass or more of a solvent having a boiling point of 55 to 200 캜,
The temperature of the water-repellent chemical liquid provided in the replacing step is set to 40 DEG C or higher and less than the boiling point of the water-repellent chemical liquid,
Wherein the wafer is a wafer comprising at least one element selected from the group consisting of titanium, tungsten, aluminum, copper, tin, tantalum, and ruthenium on the surface of the concave portion, and the water repellent chemical is represented by the following general formulas [6] to [12 And a salt thereof, and a solvent, wherein the cleaning solution contains at least one member selected from the group consisting of a compound represented by formula (I) and a salt thereof.
R ⁸ -P (= O) - (OH) _g (R ⁹ ) _2-g [6]
[In the formula [6], R ⁸ is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with a fluorine atom. R ⁹ are each independently a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with a fluorine atom. and g is an integer of 0 to 2.]
R ¹⁰ -C (═O) -X ⁴ [7]
[In the formula [7], R ¹⁰ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. X ⁴ represents a group selected from the group consisting of a fluoro group, a chloro group, a bromo group, and an iodo group.
R ¹¹ R ¹² R ¹³ N [8]
[Wherein R ¹¹ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. R ¹² is a monovalent organic group containing a hydrogen atom, a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. R ¹³ is a monovalent organic group containing a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms.
R ^{14 is} -C (= O) -X ⁵ -X ⁶ [9]
Of the formula [9], R ¹⁴ is a monovalent organic group having a carbon number of which comprises a monovalent organic group in the alkyl chain, or fluoro carbon number of from 1 to 8, which comprises a 1 to 18 hydrocarbons. X ⁵ represents an oxygen element or a sulfur element and X ⁶ represents a hydrogen atom, an alkyl group, an aromatic group, a pyridyl group, a quinolyl group, a succinimide group, a maleimide group, a benzoxazole group, a benzothiazole group, And the hydrogen atom in these groups may be substituted with an organic group.
R ¹⁵ (X ⁷ ) _h [10]
X ⁷ is at least one group selected from the group consisting of a cyclic structure including an isocyanate group, a mercapto group, an aldehyde group, a -CONHOH group and a nitrogen atom, and h is at least one group selected from the group consisting of R ¹⁵ is an organic group containing a hydrocarbon group having 1 to 18 carbon atoms or an organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms, and the above-mentioned h isocyanate group, mercapto group , A cyclic structure including an aldehyde group, a -CONHOH group, and a nitrogen element, is substituted with the same number of hydrogen atoms.
R ¹⁶ -X ⁸ [11]
Wherein X ⁸ is a cyclic structure containing a sulfur element and R ¹⁶ is a monovalent organic group containing a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a fluoroalkyl group having 1 to 8 carbon atoms Is a monovalent organic group containing a chain.]
R ^{17 is} -C (= O) -X ⁹ -C (= O) -R ¹⁸ [12]
[In the formula [12], R ¹⁷ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. R ¹⁸ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. X ⁹ represents an oxygen element or a sulfur element.] 10. The method of claim 9,
Wherein the temperature of the water-repellent chemical solution provided in the replacing step is 70 占 폚 or higher and the boiling point of the water-repellent chemical solution is lower than -10 占 폚. , At least one member selected from the group consisting of compounds represented by the following general formulas [6] to [12] and salt compounds thereof, and a solvent,
R ⁸ -P (= O) - (OH) _g (R ⁹ ) _2-g [6]
[In the formula [6], R ⁸ is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with a fluorine atom. R ⁹ is a monovalent organic group containing respectively independently of each other, some or all of the hydrogen atom is a carbon atoms which may be substituted with a fluorine element group of 1 to 18 hydrocarbons. and g is an integer of 0 to 2.]
R ¹⁰ -C (═O) -X ⁴ [7]
[In the formula [7], R ¹⁰ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. X ⁴ represents a group selected from the group consisting of a fluoro group, a chloro group, a bromo group, and an iodo group.
R ¹¹ R ¹² R ¹³ N [8]
[Wherein R ¹¹ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. R ¹² is a monovalent organic group containing a hydrogen atom, a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. R ¹³ is a monovalent organic group containing a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms.
R ^{14 is} -C (= O) -X ⁵ -X ⁶ [9]
Of the formula [9], R ¹⁴ is a monovalent organic group having a carbon number of which comprises a monovalent organic group in the alkyl chain, or fluoro carbon number of from 1 to 8, which comprises a 1 to 18 hydrocarbons. X ⁵ represents an oxygen element or a sulfur element and X ⁶ represents a hydrogen atom, an alkyl group, an aromatic group, a pyridyl group, a quinolyl group, a succinimide group, a maleimide group, a benzoxazole group, a benzothiazole group, And the hydrogen atom in these groups may be substituted with an organic group.
R ¹⁵ (X ⁷ ) _h [10]
X ⁷ is at least one group selected from the group consisting of a cyclic structure including an isocyanate group, a mercapto group, an aldehyde group, a -CONHOH group and a nitrogen atom, and h is at least one group selected from the group consisting of R ¹⁵ is an organic group containing a hydrocarbon group having 1 to 18 carbon atoms or an organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms, and the above-mentioned h isocyanate group, mercapto group , A cyclic structure including an aldehyde group, a -CONHOH group, and a nitrogen element, is substituted with the same number of hydrogen atoms.
R ¹⁶ -X ⁸ [11]
Wherein X ⁸ is a cyclic structure containing a sulfur element and R ¹⁶ is a monovalent organic group containing a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a fluoroalkyl group having 1 to 8 carbon atoms Is a monovalent organic group containing a chain.]
R ^{17 is} -C (= O) -X ⁹ -C (= O) -R ¹⁸ [12]
[In the formula [12], R ¹⁷ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. R ¹⁸ is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. X ⁹ represents an oxygen element or a sulfur element.]
The solvent is preferably at least one selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, lactone-based solvents, carbonate- Containing solvent, water, an alcohol, a derivative of a polyhydric alcohol having an OH group, or a nitrogen element-containing solvent having an NH group,
Wherein the hydrocarbons are selected from the group consisting of toluene, benzene, xylene, hexane, heptane and octane, and the esters are selected from the group consisting of ethyl acetate, propyl acetate, butyl acetate and ethyl acetoacetate, Ethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran and dioxane, and the ketones are selected from the group consisting of acetone, acetyl acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, cyclohexanone and isophorone And the halogen element-containing solvent is selected from the group consisting of perfluorocarbon, hydrofluorocarbon, hydrofluoroether, chlorocarbon, hydrochlorocarbon, chlorofluorocarbon, hydrochlorofluorocarbon, perfluoroether And perfluoropolyethers And the lactone-based solvent is selected from the group consisting of? -Butyrolactone,? -Valerolactone,? -Hexanolactone,? -Heptanolactone,? -Octanolactone, ? -undecanolactone,? -decanolactone,? -decanolactone,? -valanolactone,? -hexanolactone,? -octanolactone,? -nonanolactone, Wherein the carbonate solvent is selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and propylene carbonate, and the carbonate solvent is selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and propylene carbonate And those having no OH group among derivatives of the polyhydric alcohol are selected from the group consisting of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetic acid Ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol diethyl ether, Glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol Triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, Tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, Propylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol moiety Butyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol mono Butyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate and Glycerin triacetate, and the nitrogen element-containing solvent having no NH group is selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- And the alcohols are selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, ethylene glycol, diethylene glycol, , 2-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, triethylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol and glycerin And the derivative of the polyhydric alcohol having an OH group is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, di Ethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene Ethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, propylene glycol monoethyl ether, triethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, Methyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tri Propylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tetrapropylene glycol monomethyl ether and butylene glycol monomethyl ether Is selected from the group consisting of, nitrogen containing solvents elements having the NH group include the water repellent chemical formamide. 9. The method of claim 8,
Further comprising an acid or base,
The acid may be at least one selected from the group consisting of hydrogen chloride, sulfuric acid, perchloric acid, phosphoric acid, sulfonic acids and anhydrides thereof represented by the following formula [2], carboxylic acids and anhydrides thereof represented by the following formula [3], alkylboric acid esters, arylboric acid esters, tris (Trifluoroacetoxy) boron, trialkoxyboroxine, trifluoroboron, and silicon compound B represented by the following general formula [4]
R ² S (O) ₂ OH [2]
[In the formula [2], R ² is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms.]
R ³ COOH [3]
[In the formula [3], R ³ is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with a fluorine atom.]
(R ⁴ ) _c Si (H) _d X ² _4-cd [4]
[In the formula [4], R ⁴ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, which may be substituted with fluorine atoms in part or all of hydrogen atoms. X ² is, independently of each other, a chloro group, -OCO-R ⁵ (R ⁵ is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms), and -OS (O) _2- R ⁶ (R ⁶ represents at least one group selected from the group consisting of a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms). c is an integer of 1 to 3, d is an integer of 0 to 2, and the sum of c and d is 1 to 3.]
The base may be selected from the group consisting of ammonia, N, N, N'-tetramethylethylenediamine, triethylenediamine, dimethylaniline, alkylamine, dialkylamine, trialkylamine, pyridine, And a silicon compound C represented by the following general formula [5].
(R ⁷ ) _e Si (H) _f X ³ _4-ef [5]
[In the formula [5], R < ⁷ > is a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all hydrogen atoms may be substituted with fluorine atoms. X ³ is a monovalent functional group that is independent of each other and an element which bonds with the silicon element is nitrogen and may contain a fluorine atom or a silicon element. e is an integer of 1 to 3, f is an integer of 0 to 2, and the sum of e and f is 1 to 3.]

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