KR20210035623A - Composition for cleaning of semiconductor substrate - Google Patents

Abstract

The present invention relates to a composition for cleaning a semiconductor substrate which contains a polymer vinyl compound comprising a hydrophilic group and a hydrophobic group, and organic solvent, but, by adjusting a molar ratio of the hydrophilic group to the hydrophobic group to 1 : 0.25 to 4, separate heat or pressure is not used, so that ultra-fine particle removal power is excellent without damaging the underlying film or wiring.

Description

A composition for cleaning a semiconductor substrate TECHNICAL FIELD [COMPOSITION FOR CLEANING OF SEMICONDUCTOR SUBSTRATE]

The present invention relates to a composition for cleaning a semiconductor substrate.

In the manufacturing process of a semiconductor substrate, there is a cleaning process for removing contaminants such as particles adhering to the surface of the patterned substrate. In particular, as patterns formed in recent years have become finer and higher in aspect ratio, the size of particles is becoming smaller and smaller. As such, when the size of the particles is small, the mass of the particles is very small, and thus, due to the size effect phenomenon in which the interaction with the lower layer is significantly increased, a method for removing the particles must be developed.

Conventionally, a method of using a liquid or gas to remove such particles has been mainly used, but since it is difficult for liquid or gas to flow in the vicinity of the substrate surface or between patterns, there is a problem that the removal of particles is not performed properly. .

In addition, as a method to overcome this, a method of removing particles by ultrasonic cleaning or spraying a high-pressure cleaning solution has been attempted, but this has a problem of damaging the micropatterns or structures previously fabricated on the surface of the lower substrate, so its use is difficult. It is limited, and there is a problem that it is not easy to remove the ultrafine particles with such methods because the size effect is very large.

Therefore, it is necessary to develop a new method, not a method that adversely affects the underlying substrate such as heat, pressure, or strong acid/strong base. One of these methods is to form a polymer coating film on the surface of the substrate to capture ultrafine particles with the coating film. This is a method of removing it together with the coating film.

In this regard, Korean Laid-Open Patent Publication No. 10-2018-0059442 contains a compound having a molecular weight of 300 or more and a solvent having a polar group, a group represented by a specific formula, or a combination thereof, thereby forming a film on the substrate surface to prevent foreign substances on the substrate surface. In the removal process, a film-forming composition for cleaning a semiconductor substrate capable of efficiently removing particles on a substrate surface has been described, but this still has a problem that ultrafine particles cannot be removed.

Republic of Korea Patent Publication No. 10-2018-0059442 (2018.06.04.)

The present invention is to solve the above problems, and provides a composition for cleaning a semiconductor substrate having excellent removal power of ultrafine particles without damaging the lower film or wiring by using no separate heat or pressure for contamination of insoluble ultrafine particles. For that purpose.

The composition for cleaning a semiconductor substrate of the present invention comprises a polymeric vinyl compound containing a hydrophilic group and a hydrophobic group; And an organic solvent, wherein the molar ratio of the hydrophilic group to the hydrophobic group is 1:0.25 to 4.

The composition for cleaning a semiconductor substrate of the present invention has an advantage in that it is excellent in removing power of insoluble ultrafine particles while preventing damage to the lower film or wiring due to the use of no separate heat or pressure.

In the present invention, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In the present invention, the heterocyclic group may be monocyclic or polycyclic, and may be aromatic, aliphatic, or condensed rings of aromatic and aliphatic.

In the present invention, the hetero atom may be one or more selected from O, S, Se, N, or Si.

Hereinafter, the present invention will be described in more detail.

A composition for cleaning a semiconductor substrate according to an aspect of the present invention includes a polymer vinyl compound including a hydrophilic group and a hydrophobic group; And an organic solvent; but, by adjusting the molar ratio of the hydrophilic group to the hydrophobic group to 1:0.25 to 4, there is an advantage in that the removal power of ultrafine particles is excellent without damage to the lower film or wiring because no separate heat or pressure is used.

Specifically, the method of removing ultra-fine particles using the cleaning composition is by coating the cleaning composition on the surface of a substrate to form a coating film, thereby capturing the ultra-fine particles, and using an aqueous solution (for example, ultrapure water). Then, the coating layer is swelled to cause cracking or peeling (Lift-Off) of the coating layer, and the coating layer is firstly removed by physically rotating it, and then the coating layer is completely removed using an organic solvent.

At this time, since the cleaning composition of the present invention contains a hydrophilic group, it has an excellent ability to absorb ultrapure water, thereby facilitating swelling of the coating film, thereby facilitating removal of the coating film. Removal of the coating film also has an advantageous advantage. In addition, the cleaning composition of the present invention adjusts the molar ratio of the hydrophilic group to the hydrophobic group to 1:0.25 to 4, so that when the composition is applied on a substrate, the coating property is good and the capturing power of ultrafine particles is excellent. Even during the removal process of the composition coating film using a solvent, the coating film is not completely dissolved in an aqueous solution or an organic solvent, so that trapped fine particles can be completely removed together with the coating film without missing. When the molar ratio between the hydrophilic group and the hydrophobic group is out of the molar ratio, the affinity with the aqueous solution or organic solvent such as ultrapure water is excessively increased. It can be re-adsorbed to the surface of the substrate again.

The molar ratio of the hydrophilic group and the hydrophobic group may be preferably 1:0.4 to 2.3, more preferably 1:0.7 to 1.5.When the hydrophilic group and the hydrophobic group satisfy a preferred molar ratio, the removal power of the ultrafine particles is more There is an advantage that can be improved.

The cleaning composition according to an aspect of the present invention includes a polymer vinyl compound.

As described above, since the cleaning composition of the present invention contains a vinyl copolymer other than a (meth)acrylate copolymer, it is not easy to control hydrophilicity or hydrophobicity by a hydrophilic group or a hydrophobic group due to the presence of an excess structure such as an ester bonding portion. Unlike (meth)acrylate copolymers, vinyl copolymers have an advantage in that they do not have an excess structure, so that the characteristics of introduced pendant groups (hydrophilic groups or hydrophobic groups) are easily expressed.

The hydrophilic group included in the polymeric vinyl compound may include, for example, a structure derived from a vinyl compound having a hydroxy group, a carboxyl group, an acid anhydride, or an amide group. According to an embodiment of the present invention, the following formulas 1 to 7 It may contain one or more selected from the functional groups shown.

[Formula 1]

[Formula 2]

[Formula 3]

(In Chemical Formula 3,

R ₁ and R ₂ are each independently hydrogen, a linear or branched C1 to C4 alkyl group, or a C6 to C10 aryl group.)

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

(In Chemical Formula 7, n is an integer of 1 to 3.)

When the polymeric vinyl compound contains at least one hydrophilic group in Formulas 1 to 7, water molecules easily penetrate into the polymer matrix to cause swelling in the process of treating the polymer coating film with an aqueous solution (eg, ultrapure water). It plays a role of helping and has the advantage of promoting the lift-off behavior in which the swollen polymer coating film is peeled off together with the trapped ultrafine particles due to the occurrence of compressive stress due to the expansion of the coating film.

The hydrophobic group included in the polymeric vinyl compound may be, for example, a structure derived from a vinyl compound having an alkyl, an aromatic ring, or an aromatic ester group, and according to an embodiment of the present invention, a functional group represented by the following Formulas 8 to 11 It may include one or more selected from.

[Formula 8]

(In Chemical Formula 8,

R ₃ is hydrogen, a linear or branched C1 to C18 alkyl group, or a C6 to C10 aryl group.)

[Formula 9]

(In Chemical Formula 9,

R ₄ is a linear or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom.)

[Formula 10]

(In Chemical Formula 10,

R ₅ is hydrogen, a halogen atom, or a straight or branched C1 to C4 alkyl group,

M is an integer of 0 to 6.)

[Formula 11]

(In Chemical Formula 11,

R ₆ is hydrogen, a straight or branched C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C6 to C10 aryl group, a C1 to C12 carbonyl group, or a carboxyl group.)

When the polymeric vinyl compound contains at least one hydrophobic group in Formulas 8 to 11, the swollen polymer coating film is not completely dissolved in the process of treating the polymer coating film with an aqueous solution (for example, ultrapure water) and compressive stress is generated. It may be easier to adjust the overall properties of the polymer coating film so that the polymer coating film that has started to be lifted from the substrate is easily peeled off due to interfacial penetration in the aqueous solution washing process, whereby the polymer coating film swells by the aqueous solution, but is captured when completely dissolved. There is an advantage in that it is easier to prevent the problem of re-adhering to the substrate due to the contamination of contaminants, and also exhibits appropriate solubility in the cleaning step using an organic solvent, so that the coating film can be completely removed without residue.

In addition, the polymeric vinyl compound may include one or more selected from the group consisting of compounds represented by the following Chemical Formulas 12 to 21.

[Formula 12]

(In Chemical Formula 12,

R ₇ is hydrogen, a straight or branched C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C6 to C10 aryl group, a C1 to C12 carbonyl group, or a carboxyl group,

The molar ratio of b ₁ :a ₁ is 1:0.25 to 4.)

[Formula 13]

(In Chemical Formula 13,

R ₈ is hydrogen, a linear or branched C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C6 to C10 aryl group, a C1 to C12 carbonyl group, or a carboxyl group,

The molar ratio of b ₂ :a ₂ is 1:0.25 to 4.)

[Formula 14]

(In Chemical Formula 14,

R ₉ is a linear or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,

The molar ratio of b ₃ :a ₃ is 1:0.25 to 4.)

[Formula 15]

(In Chemical Formula 15,

R ₁₀ is a linear or branched C1 to C18 alkyl group, or a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,

The molar ratio of b ₄ :a ₄ is 1:0.25 to 4.)

[Formula 16]

(In Chemical Formula 16,

R ₁₁ is hydrogen, a straight or branched C1 to C12 alkyl group, a C1 to C12 alkoxy group, or a C6 to C10 aryl group, a C1 to C12 carbonyl group, or a carboxyl group,

The molar ratio of b ₅ :a ₅ is 1:0.25 to 4.)

[Formula 17]

(In Chemical Formula 17,

R ₁₂ is hydrogen, a straight or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,

The molar ratio of b ₆ : a ₆ is 1:0.25 to 4.)

[Formula 18]

(In Chemical Formula 18,

R ₁₃ and R ₁₄ are each independently a straight or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,

The molar ratio of b ₇ :(a ₇ + a ₈ ) is 1:0.25 to 4.)

[Formula 19]

(In Chemical Formula 19,

R ₁₅ and R ₁₆ are each independently a straight or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,

The molar ratio of b ₈ :(a ₉ + a ₁₀ ) is 1:0.25 to 4.)

[Formula 20]

(In Chemical Formula 20,

R ₁₇ and R ₁₈ are each independently a straight or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a heterocyclic group containing a hetero atom,

The molar ratio of b ₉ :(a ₁₁ + a ₁₂ ) is 1:0.25 to 4.)

[Formula 21]

(In Chemical Formula 21,

R ₁₉ is hydrogen, a straight or branched C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C6 to C10 aryl group, a C1 to C12 carbonyl group, or a carboxyl group,

R ₂₀ is a straight or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,

The molar ratio of b ₁₀ :(a ₁₃ + a ₁₄ ) is 1:0.25 to 4.)

According to an embodiment of the present invention, the polymeric vinyl compound is contained in an amount of 0.5 to 50% by weight, preferably 2 to 15% by weight, and more preferably 4 to 10% by weight, based on 100% by weight of the total composition containing the same. I can. If the above range is satisfied, there is an advantage in that it is easy to form a target coating film by exerting appropriate solubility and coating properties, and if it is contained within the above range, a coating film of an appropriate thickness to facilitate removal of fine particles and easy cleaning of the coating film. Difficulty may occur in forming the film, and if it exceeds the above range, the thickness of the coating film becomes too thick, so that smooth removal in the cleaning step may be difficult.

The cleaning composition according to an aspect of the present invention includes an organic solvent.

The organic solvent serves to mix the constituent components included together, and preferably, a water-soluble organic solvent may be used, and according to an embodiment of the present invention, the -OH group may be contained in the molecule. As described above, in the case of an organic solvent containing an -OH group, it has hydrophilicity. When the cleaning composition of the present invention is applied on a substrate to form a coating film, it does not use separate heat or pressure for drying the composition. Even after the solvent is completely formed, a certain amount of the organic solvent remains. In this case, when swelling with an aqueous solution to remove the coating film, if the organic solvent has hydrophilicity, there is an advantage that swelling by the aqueous solution may be easier.

The organic solvent containing the -OH group is, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl Ether, polyethylene glycol monoethyl ether, polyethylene glycol motoisopropyl ether, polyethylene glycol monobutyl ether, propylene glycol methyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethyl lactate, 3-methoxy-1 -Butanol, ethyl 3-hydroxybutyrate, and the like, but are not limited thereto, and these may be used alone or in combination of two or more.

According to an embodiment of the present invention, the organic solvent is contained in 50 to 99.5% by weight, preferably 80 to 95% by weight, more preferably 90 to 95% by weight, based on 100% by weight of the total composition containing the same. I can. When the content of the organic solvent satisfies the above range, there is an advantage in that it is easy to form a target coating film by properly dissolving the polymer and additives to exhibit coating properties. Due to the thickening, there may be a problem in that smooth removal of the coating film is difficult in the cleaning step.If the above range is exceeded, particulates, that is, contaminants can be easily captured and cleaned in the rotational speed section used in the general spin coating process. Difficulty may occur in forming a coating film having an appropriate thickness, which is easy to remove the coating film during the time period.

The cleaning composition according to an embodiment of the present invention may further include a water-soluble monomolecular compound. As described above, when the cleaning composition further includes a water-soluble monomolecular compound containing a hydrophilic group, it may be easier for the aqueous solution to penetrate into the coating film when contacted with the aqueous solution to remove the coating film formed from the cleaning composition. There is an advantage that the swelling of the can become more advantageous.

Further, according to an embodiment of the present invention, the water-soluble monomolecular compound is an acidic compound containing two or more acidic groups in one molecule; Amine compounds containing at least one -OH group in one molecule; And polyhydric alcohol; may include one or more selected from the group containing, in this case, there is an advantage that the coating film permeability of the aqueous solution can be improved.

The acidic group refers to an acidic functional group, for example, a strong acidic group such as a sulfonic acid group and a phosphoric acid group; Weakly acidic groups such as carboxyl groups, etc., but are not limited thereto .

The acidic compounds containing two or more acidic groups are, for example, oxalic acid, malonic acid, maleic acid, glutaric acid, citric acid, ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, 1, 2-cyclohexanedicarboxylic acid, benzene-1,2-dicarboxylic acid (also referred to as "phthalic acid"), benzene-1,3-dicarboxylic acid (also referred to as "isophthalic acid"), benzene-1,4-dicarboxylic acid ( An aromatic compound having two acidic groups of "terephthalic acid"), biphenyl-2,2'-dicarboxylic acid, 2-(carboxymethyl)benzoic acid, 3-(carboxymethyl)benzoic acid, and 4-(carboxymethyl)benzoic acid; Pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole-2,4-dicarboxylic acid, imidazole-2 ,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid, thiophene-2,3-dicarboxylic acid, thiophene-2 ,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole-2,5-dicarboxylic acid, thiazole-4 ,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole-3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3, 4-thiadiazole-2,5-dicarboxylic acid, (5-mercapto-1,2,4-thiadiazole-3-ylthio)acetic acid, (5-mercapto-1,3,4 -Thiadiazol-2-ylthio)acetic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, Pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine -4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine-2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine- And heterocyclic compounds having two acidic groups such as 2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, and triazine-2,4-dicarboxylic acid. It is not limited.

The amine compound containing at least one -OH group in the molecule is, for example, choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, isopropanolamine, 2-aminoethanol, 2-(ethylamino) Ethanol, 2-(methylamino)ethanol, N-methyl diethanolamine, N,N-dimethylethanolamine, N,N-diethylaminoethanol, 2-(2-aminoethylamino)-1-ethanol, 1- Amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, 4-amino-1-butanol, dibutanolamine, (methoxymethyl) diethanolamine, (hydroxyethyloxymethyl) Diethylamine, methyl(methoxymethyl)aminoethanol, methyl(methoxymethyl)aminoethanol, methyl(butoxymethyl)aminoethanol, 2-(2-aminoethoxy)ethanol, dimethylhydroxylamine, diethylhydr Roxylamine, dibutylhydroxylamine, 1-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)methylpiperazine, N-(2-hydroxyethyl)morpholine, N-(3 Amines such as -hydroxypropyl)morpholine may be mentioned, but the present invention is not limited thereto.

The polyhydric alcohol is, for example, acetone oxime, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propane diol, dipropylene glycol, polypropylene glycol, glycerol, polyglycerin, butanediol, Heptanediol, hexanediol trimethylolpropane, pentaerythritol, sorbitol, and the like, but are not limited thereto.

According to an embodiment of the present invention, the water-soluble monomolecular compound may be included in an amount of 10 to 100 parts by weight based on a total of 100 parts by weight of the polymer vinyl compound included together, preferably 15 to 80 parts by weight, more preferably It may be included in 20 to 60 parts by weight. If it is contained within the above range, the effect of promoting the swelling action of the coating film by the aqueous solution may be somewhat impaired, and if it exceeds the above range, miscibility between the components may occur, resulting in precipitation in the composition, and the composition Surface abnormalities such as stains or cracks may occur on the coating film formed with

Hereinafter, preferred embodiments are presented to aid in the understanding of the present invention, but the following examples are only illustrative of the present invention, and that various changes and modifications are possible within the scope of the present invention and the scope of the technical idea are obvious to those skilled in the art. , It is natural that such modifications and modifications fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "parts" indicating the content are based on weight unless otherwise specified.

Synthesis example : Synthesis of polymer vinyl compound

Synthesis example One

A 1L flask equipped with a reflux condenser, dropping funnel, and stirrer was placed in a nitrogen atmosphere, 200 g of propylene glycol monomethyl ether was introduced, the temperature was raised to 100°C, and 16.2 g (0.10 mol) of acetoxystyrene and 93.7 g (0.90 mol) of styrene were introduced. Mol) was added, followed by stirring, and then a solution in which 1.8 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 150 g of propylene glycol monomethyl ether was added to the reaction solution for 2 hours from a dropping funnel. It was added dropwise to the flask over and continued stirring at 100° C. for 5 hours. After the reaction is completed, the acetyl group is deprotected under acidic conditions, converted into a polymer having a hydroxy styrene structure, precipitated in a solution, and then re-dissolved in propylene glycol monomethyl ether to have a weight average molecular weight of 5,200 and a molecular weight distribution (Mw/Mn). ) Was 1.55 to obtain a polymeric vinyl compound A-1.

Synthesis example 2

Synthesis was performed in the same manner as in Synthesis Example 1, except that 162.2 g (1.00 mol) of acetoxystyrene was reacted except for styrene, and the weight average molecular weight was 5,530, and the molecular weight distribution ( Mw/Mn) was 1.49 to obtain a polymeric vinyl compound A-2.

Synthesis example 3

The same conditions and composition as in Synthesis Example 1 were used, except that 48.7 g (0.30 mol) of acetoxystyrene and 72.9 g (0.70 mol) of styrene were reacted, and the synthesis was conducted in the same manner, and the weight average molecular weight was 3,700. , Molecular weight distribution (Mw/Mn) was 1.48 to obtain a polymeric vinyl compound A-3.

Synthesis example 4

Synthesis was performed in the same manner as in Synthesis Example 1, except that 81.1 g (0.50 mol) of acetoxystyrene and 52.1 g (0.50 mol) of styrene were reacted, and the weight average molecular weight was 3,350. , Molecular weight distribution (Mw/Mn) was 1.58 to obtain a polymeric vinyl compound A-4.

Synthesis example 5

The same conditions and configuration as in Synthesis Example 1 were used, except for reacting 97.3 g (0.60 mol) of acetoxystyrene and 41.7 g (0.40 mol) of styrene, and the synthesis was conducted in the same manner, and the weight average molecular weight was 3,840. , Molecular weight distribution (Mw/Mn) was 1.48 to obtain a polymeric vinyl compound A-5.

Synthesis example 6

Synthesis was performed in the same manner as in Synthesis Example 1, except that 129.8 g (0.80 mol) of acetoxystyrene and 20.8 g (0.20 mol) of styrene were reacted, and the weight average molecular weight was 5,200. , Molecular weight distribution (Mw/Mn) was 1.62 to obtain a polymer vinyl compound A-6.

Synthesis example 7

After replacing the inside of a 1L flask equipped with a reflux condenser, a dropping funnel, and a stirrer with a nitrogen atmosphere, introducing 200 g of propylene glycol monomethyl ether acetate, raising the temperature to 100°C, and adding 162.2 g (1.00 mol) of acetoxystyrene. Next, a solution obtained by dissolving 1.8 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 150 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over 1 hour, and at 100°C for 3 more hours. Stirring was continued.

After the polymerization reaction is completed, the acetyl group is deprotected under acidic conditions, and then a polymer having a hydroxystyrene structure is obtained through reprecipitation. After dissolving it in propylene glycol monomethyl ether acetate, 31.7 g (0.44 g) of ethyl vinyl ether at room temperature. Mol) to obtain a polymeric vinyl compound A-7 in which the terminal of some hydroxy groups was protected with acetal derived from ethyl vinyl ether. For the purification of the obtained compound, it was re-dissolved in propylene glycol monomethyl ether after reprecipitation to adjust the solid content to 25 wt%. At this time, the weight average molecular weight of the obtained compound was 11,400, and the molecular weight distribution (Mw/Mn) was 1.71.

Synthesis example 8

In a 1L flask equipped with a reflux condenser, dropping funnel, and stirrer, 200 g of propylene glycol monomethyl ether was introduced under a nitrogen atmosphere, the temperature was raised to 100°C, and then 81.1 g (0.50 mol) of acetoxystyrene and 67.1 g of methoxystyrene After (0.50 mol) was added and stirred, a solution in which 1.8 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 150 g of propylene glycol monomethyl ether was added to the reaction solution from a dropping funnel. It was dripped into the flask over 2 hours, and stirring was continued at 100 degreeC for 5 more hours. After the reaction was completed, the acetyl group was deprotected under acidic conditions to finally obtain a polymeric vinyl compound A-8 having methoxystyrene and hydroxystyrene structures. The weight average molecular weight of the compound thus obtained was 3,500, and the molecular weight distribution (Mw/Mn) was 1.60.

Synthesis example 9

Under the same conditions as in Synthesis Example 1, 48.7 g (0.35 mol) of N-vinyl caprolactam and 56.0 g (0.65 mol) of vinyl acetate were reacted to have a weight average molecular weight of 7,300, and a molecular weight distribution (Mw/Mn) of 1.65 polymer vinyl. Compound A-9 was obtained.

Synthesis example 10

In the same conditions as in Synthesis Example 1, a polymer having a weight average molecular weight of 7,100 and a molecular weight distribution (Mw/Mn) of 1.68 by reacting 69.6 g (0.50 mol) of N-vinyl caprolactam and 43.1 g (0.50 mol) of vinyl acetate Vinyl compound A-10 was obtained.

Synthesis example 11

Under the same conditions as in Synthesis Example 1, 69.6 g (0.50 mol) of N-vinyl caprolactam and 71.1 g (0.50 mol) of vinyl hexanoate were reacted to have a weight average molecular weight of 6,800, and a molecular weight distribution (Mw/Mn) of 1.75. Phosphorus polymeric vinyl compound A-11 was obtained.

Synthesis example 12

In the same conditions as in Synthesis Example 1, 69.6 g (0.50 mol) of N-vinyl caprolactam, 35.6 g (0.25 mol) of vinyl hexanoate, and 21.5 g (0.25 mol) of vinyl acetate were reacted to have a weight average molecular weight of 4,700. , Molecular weight distribution (Mw/Mn) was 1.91 to obtain a polymeric vinyl compound A-12.

Synthesis example 13

Under the same conditions as in Synthesis Example 1, 52.1 g (0.50 mol) of styrene and 74.1 g (0.50 mol) of 4-vinylbenzoic acid were reacted to have a weight average molecular weight of 7,500, and a molecular weight distribution (Mw/Mn) of 1.55. I got A-13.

Synthesis example 14

Polymeric vinyl compound A having a weight average molecular weight of 4,200 and a molecular weight distribution (Mw/Mn) of 1.87 by reacting 62.5 g (0.60 mol) of styrene and 39.2 g (0.40 mol) of maleic anhydride under the same conditions as in Synthesis Example 1 I got -14.

Synthesis example 15

Polymeric vinyl compound A having a weight average molecular weight of 3,900 and a molecular weight distribution (Mw/Mn) of 1.69 by reacting 52.1 g (0.50 mol) of styrene and 49.0 g (0.50 mol) of maleic anhydride under the same conditions as in Synthesis Example 1 I got -15.

Synthesis example 16

Under the same conditions as in Synthesis Example 1, 49.0 g (0.50 mol) of maleic anhydride, 26.0 g (0.25 mol) of styrene, and 35.6 g (0.25 mol) of vinyl hexanoate were reacted to have a weight average molecular weight of 5,100, and molecular weight distribution. (Mw/Mn) obtained a polymeric vinyl compound A-16 of 1.76.

Synthesis example 17

Under the same conditions as in Synthesis Example 1, 74.1 g (0.50 mol) of vinyl benzoate and 49.0 g (0.50 mol) of maleic anhydride were reacted to have a weight average molecular weight of 7,300, and a molecular weight distribution (Mw/Mn) of 1.47. Compound A-17 was obtained.

Example : Preparation of detergent composition

A detergent composition was prepared with the composition and contents shown in Table 1 or Table 2 below.

(Unit: wt%) division
Example One 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Polymer vinyl compound (A) A-3 4.39 3.91 3.21 - - - - - - - - - - - - - - A-4 - - - 3.91 - - - - - - - - - - - - - A-5 - - - - 3.91 - - - - - - - - - - - - A-6 - - - - - 3.91 - - - - - - - - - - - A-7 - - - - - - 3.91 - - - - - - - - - - A-8 - - - - - - - 3.91 - - - - - - - - - A-9 - - - - - - - - 3.91 - - - - - - - - A-10 - - - - - - - - - 3.91 - - - - - - - A-11 - - - - - - - - - - 3.91 - - - - - - A-12 - - - - - - - - - - - 3.91 - - - - - A-13 - - - - - - - - - - - - 3.91 - - - - A-14 - - - - - - - - - - - - - 3.91 - - - A-15 - - - - - - - - - - - - - - 3.91 - - A-16 - - - - - - - - - - - - - - - 3.91 - A-17 - - - - - - - - - - - - - - - - 3.91 Water-soluble monomolecular compound (B) B-1 - - - - - - - - - - - - - - - - 1.09 B-2 0.61 1.09 1.79 1.09 1.09 1.09 1.09 1.09 - - - - 1.09 1.09 1.09 1.09 - B-3 - - - - - - - - 1.09 1.09 1.09 1.09 - - - - - Organic solvent (C) C-1 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 C-2 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 A-3: Polymeric vinyl compound of Synthesis Example 3
A-4: Polymeric vinyl compound of Synthesis Example 4
A-5: Polymeric vinyl compound of Synthesis Example 5
A-6: Polymeric vinyl compound of Synthesis Example 6
A-7: Polymeric vinyl compound of Synthesis Example 7
A-8: Polymeric vinyl compound of Synthesis Example 8
A-9: Polymeric vinyl compound of Synthesis Example 9
A-10: Polymeric vinyl compound of Synthesis Example 10
A-11: Polymeric vinyl compound of Synthesis Example 11
A-12: Polymeric vinyl compound of Synthesis Example 12
A-13: Polymeric vinyl compound of Synthesis Example 13
A-14: Polymeric vinyl compound of Synthesis Example 14
A-15: Polymeric vinyl compound of Synthesis Example 15
A-16: Polymeric vinyl compound of Synthesis Example 16
A-17: Polymeric vinyl compound of Synthesis Example 17
B-1: oxalic acid
B-2: malonic acid
B-3: triethanolamine
C-1: propylene glycol methyl ether (PGME)
C-2: propylene glycol mono methyl ether acetate (PGMEA)

(Unit: wt%) division
Example 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 Polymer vinyl compound (A) A-3 - - - - - 3.91 3.91 3.91 3.91 3.91 3.91 3.91 3.91 3.91 3.91 3.91 - A-4 5.00 - - - - - - - - - - - - - - - - A-7 - - - - - - - - - - - - - - - - 3.91 A-10 - 5.00 - - - - - - - - - - - - - - - A-11 - - 5.00 - - - - - - - - - - - - - - A-12 - - - 5.00 - - - - - - - - - - - - - A-15 - - - - 5.00 - - - - - - - - - - - - Water-soluble monomolecular compound (B) B-1 - - - - - 1.09 - - - - - - - - - - - B-3 - - - - - - - - - 1.09 - - - - - - 1.09 B-4 - - - - - - 1.09 - - - - - - - - - - B-5 - - - - - - - 1.09 - - - - - - - - - B-6 - - - - - - - - 1.09 - - - - - - - - B-7 - - - - - - - - - - 1.09 - - - - - - B-8 - - - - - - - - - - - 1.09 - - - - - B-9 - - - - - - - - - - - - 1.09 - - - - B-10 - - - - - - - - - - - - - 1.09 - - - B-11 - - - - - - - - - - - - - - 1.09- - - B-12 - - - - - - - - - - - - - - - 1.09 - Organic solvent (C) C-1 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 C-2 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 A-3: Polymeric vinyl compound of Synthesis Example 3
A-4: Polymeric vinyl compound of Synthesis Example 4
A-7: Polymeric vinyl compound of Synthesis Example 7
A-10: Polymeric vinyl compound of Synthesis Example 10
A-11: Polymeric vinyl compound of Synthesis Example 11
A-12: Polymeric vinyl compound of Synthesis Example 12
A-15: Polymeric vinyl compound of Synthesis Example 15
B-1: oxalic acid
B-3: triethanolamine
B-4: maleic acid
B-5: glutaric acid
B-6: citric acid
B-7: diethanolamine
B-8: monoethanolamine
B-9: isopropanolamine
B-10: acetoxime
B-11: glycerol
B-12: diethylene glycol
C-1: propylene glycol methyl ether (PGME)
C-2: propylene glycol monomethyl ether acetate (PGMEA)

Comparative example : Preparation of detergent composition

A detergent composition was prepared with the composition and contents shown in Table 3 below.

(Unit: wt%) division
Comparative example One 2 3 4 5 6 7 8 9 10 11 12 13 14 Polymer vinyl compound (A) A-1 5.00 3.91 3.91 3.91 - - - - - - - - - - A-2 - - - - 5.00 3.91 3.91 3.91 - - - - - - A-18 - - - - - - - - 3.91 - - 3.91 - - A-19 - - - - - - - - - 3.91 - - 3.91 - A-20 - - - - - - - - - - 3.91 - - 3.91 Water-soluble monomolecular compound (B) B-2 - 1.09 - - - 1.09 - - 1.09 1.09 1.09 - - - B-3 - - 1.09 - - - 1.09 - - - - 1.09 1.09 1.09 B-11 - - - 1.09 - - - 1.09 - - - - - - Organic solvent (C) C-1 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 80.75 C-2 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 14.25 A-1: Polymeric vinyl compound of Synthesis Example 1
A-2: Polymeric vinyl compound of Synthesis Example 2
A-18: polyvinylpyrrolidone
A-19: polyvinylalcohol
A-20: polyvinylacetate
B-2: malonic acid
B-3: triethanolamine
B-11: glycerol
C-1: propylene glycol methyl ether (PGME)
C-2: propylene glycol monomethyl ether acetate (PGMEA)

Experimental example One: Coating properties evaluation

After coating the cleaning composition prepared in Examples and Comparative Examples on the surface of an 8” Si wafer, it was spin-coated to form a 2000Å coating film, and left to stand in a clean room for 90 seconds to dry.

The surface of the formed coating film was visually checked to confirm that there was no abnormality in the coating film, and the results are shown in Table 4 below. In this case, a normal case in which no defects or abnormalities could be confirmed through inspection was indicated as OK, and an abnormal case in which stains on the surface of the coating film, coating was not properly formed or cracks appeared on the edge was indicated as NG.

Experimental example 2: Evaluation of particulate removal efficiency

After immersing an 8” Si wafer in a mixed solution of aqueous ammonia and hydrogen peroxide (mixed 1 to 4 and diluted with 10% ultrapure water), rinsed at 60℃ for 5 minutes, rinsed with ultrapure water, and then dried. Basic cleaning was performed, followed by dispersion in 0.1 wt% of 20 nm-sized silica particles in 99.9 wt% of ultrapure water, coating on the surface of the Si wafer, and drying by spinning. Then, after counting the number of fine particles in the entire surface of the 8" wafer with Surfscan SP1 (manufactured by KLA Tencor), coating the cleaning composition prepared in Examples and Comparative Examples, and then spin coating to form a coating film of 2000Å. The resulting coating film was left in a clean room for a second and dried by spraying ultrapure water for 2 minutes at a flow rate of 2L per minute while rotating the film at 500 rpm to peel off the film, and then the polymer residue remaining on the surface was rotated at 500 rpm and the substrate was rotated at 500 rpm. A solvent (Propylene glycol monomethylether + Ethoxyethylpropionate + n-butyl acetate = 70wt% + 20wt% + 10wt%) was sprayed at a flow rate of 0.5 L per minute and rinsed. Was counted, and the amount of change (removal rate) before/after cleaning was calculated using Equation 1 below, and the result is described in the following 4 (monitoring for a particle size of 160 to 200 nm)

[Equation 1]

Removal rate (PRE, %) = [(Number of particles before cleaning-Number of particles after cleaning)/Number of particles before cleaning] × 100

Experimental example 3: Self-cleaning power evaluation

This experiment was conducted to confirm whether the respective cleaning compositions prepared in the above Examples and Comparative Examples themselves remained on the substrate to cause contamination.

After immersing an 8” Si wafer in a mixed solution of aqueous ammonia and hydrogen peroxide (mixed 1 to 4 and diluted with 10% ultrapure water), rinsed at 60℃ for 5 minutes, then rinsed with ultrapure water and then dried. After performing basic cleaning, it was left in the clean room for 24 hours. After counting the number of fine particles in the entire surface of the 8" wafer with Surfscan SP1 (manufactured by KLA Tencor), the cleaned surface was then coated with the cleaning composition prepared in the above Examples and Comparative Examples, and then spin-coated to form a 2000Å coating film. The obtained coating film was rotated at 500 rpm and sprayed with ultrapure water at a flow rate of 2 L per minute for 2 minutes to peel off the coating film, and then the residue remaining on the surface was rotated at 500 rpm and 2-Propanol was added at 0.5 L per minute. The substrate was rinsed by spraying at a flow rate.After the cleaning was completed, the number of fine particles on the surface was counted again using Surfscan SP1, and the self-cleaning power was checked using the amount of change before/after the cleaning, and the result was obtained. It is shown in Table 4 below.

At this time, if the number of fine particles before/after cleaning increases to within 1000, it is considered as a natural increase according to the process, and it is judged that there is no problem, and the range that exceeds 1000 or the measuring device can count is determined. If the increase is exceeded, it is judged that the self-cleaning power is not good.

Coating properties
evaluation particle Removal efficiency evaluation Self-cleaning power evaluation Before After Removal rate( % ) Before After Example One OK 12650 1896 85 33 171 2 OK 10607 438 96 51 82 3 OK 16522 1641 90 47 211 4 OK 14660 1898 87 10 267 5 OK 14660 1843 87 37 612 6 OK 16531 4563 72 29 887 7 OK 10558 716 93 5 358 8 OK 13004 678 95 12 102 9 OK 12880 1827 86 16 467 10 OK 16506 2031 88 11 541 11 OK 14802 871 94 7 93 12 OK 11561 662 94 37 138 13 OK 12034 1428 88 32 294 14 OK 13557 1351 90 53 540 15 OK 15232 931 94 5 235 16 OK 19623 1008 95 2 87 17 OK 20037 1152 94 9 64 18 OK 12355 2942 76 2 983 19 OK 17142 4353 75 14 1305 20 OK 9971 2415 76 31 1562 21 OK 13642 3787 72 29 1786 22 OK 15330 4167 73 67 1022 23 OK 9268 981 89 11 452 24 OK 11351 576 95 3 86 25 OK 13601 1642 88 13 198 26 OK 10024 593 94 3 69 27 OK 9865 231 98 One 43 28 OK 12441 1523 88 16 855 29 OK 10049 1939 81 10 552 30 OK 9963 1453 85 21 629 31 OK 13244 1296 90 7 78 32 OK 10360 1080 90 6 136 33 OK 14202 1897 87 4 322 34 OK 11540 357 97 2 54 Comparative example One OK 9793 Not measurable Not measurable 7 Not measurable 2 OK 12463 Not measurable Not measurable 23 Not measurable 3 NG 13350 Not measurable Not measurable 11 Not measurable 4 NG 9681 Not measurable Not measurable 46 Not measurable 5 OK 11134 Not measurable Not measurable 19 Not measurable 6 OK 9691 Not measurable Not measurable 34 Not measurable 7 OK 12502 Not measurable Not measurable One Not measurable 8 OK 10260 Not measurable Not measurable 3 Not measurable 9 NG 9960 Not measurable Not measurable 10 Not measurable 10 OK 13561 Not measurable Not measurable 17 Not measurable 11 OK 10085 Not measurable Not measurable 22 Not measurable 12 NG 12304 Not measurable Not measurable 8 Not measurable 13 NG 11680 Not measurable Not measurable 47 Not measurable 14 OK 15066 Not measurable Not measurable 19 Not measurable *If the number of particles cannot be counted due to the occurrence of a residual film or the number of particles exceeding the measurement limit due to a rapid increase in the number of particles due to residues, it is indicated as'not measurable'.

Referring to Table 4, in the case of Examples 1 to 34 that satisfy all the conditions of the present invention, coating properties are superior to those of Comparative Examples 1 to 14 which do not satisfy any of the conditions of the present invention, and in particular, particulate removal power or It was confirmed that self-cleaning power was excellent.

In addition, as suggested by preferred examples in the present invention, when a water-soluble monomolecular compound is further included (Examples 1 to 17, 23 to 34) When no water-soluble monomolecular compound is further included (Examples 18 to 22 It was confirmed that the particle removal power was more improved than ).

Claims (10)

A polymer vinyl compound containing a hydrophilic group and a hydrophobic group; And an organic solvent; including,
The composition for cleaning a semiconductor substrate in which the molar ratio of the hydrophilic group to the hydrophobic group is 1:0.25 to 4. The method of claim 1,
The cleaning composition further comprises a water-soluble monomolecular compound. The method of claim 2,
The water-soluble monomolecular compound is an acidic compound containing two or more acidic groups in one molecule; Amine compounds containing at least one -OH group in one molecule; And polyhydric alcohol; A composition for cleaning a semiconductor substrate comprising at least one selected from the group containing. The method of claim 1,
The hydrophilic group is a composition for cleaning a semiconductor substrate comprising at least one selected from functional groups represented by the following Chemical Formulas 1 to 7.
[Formula 1]

[Formula 2]

[Formula 3]

(In Chemical Formula 3,
R ₁ and R ₂ are each independently hydrogen, a linear or branched C1 to C4 alkyl group, or a C6 to C10 aryl group.)
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

(In Chemical Formula 7, n is an integer of 1 to 3.) The method of claim 1,
The hydrophobic group is a cleaning composition for a semiconductor substrate, characterized in that it contains at least one or more of the functional groups represented by the following formulas 8 to 11.
[Formula 8]

(In Chemical Formula 8,
R ₃ is hydrogen, a linear or branched C1 to C18 alkyl group, or a C6 to C10 aryl group.)
[Formula 9]

(In Chemical Formula 9,
R ₄ is a straight or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom.)
[Formula 10]

(In Chemical Formula 10,
R ₅ is hydrogen, a halogen atom, or a straight or branched C1 to C4 alkyl group,
M is an integer of 0 to 6.)
[Formula 11]

(In Chemical Formula 11,
R ₆ is hydrogen, a straight or branched C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C6 to C10 aryl group, a C1 to C12 carbonyl group, or a carboxyl group.) The method of claim 1,
The polymeric vinyl compound is a composition for cleaning a semiconductor substrate comprising at least one selected from the group consisting of compounds represented by the following Chemical Formulas 12 to 21.
[Formula 12]

(In Chemical Formula 12,
R ₇ is hydrogen, a straight or branched C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C6 to C10 aryl group, a C1 to C12 carbonyl group, or a carboxyl group,
The molar ratio of b ₁ :a ₁ is 1:0.25 to 4.)
[Formula 13]

(In Chemical Formula 13,
R ₈ is hydrogen, a linear or branched C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C6 to C10 aryl group, a C1 to C12 carbonyl group, or a carboxyl group,
The molar ratio of b ₂ :a ₂ is 1:0.25 to 4.)
[Formula 14]

(In Chemical Formula 14,
R ₉ is a linear or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,
The molar ratio of b ₃ :a ₃ is 1:0.25 to 4.)
[Formula 15]

(In Chemical Formula 15,
R ₁₀ is a straight or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,
The molar ratio of b ₄ :a ₄ is 1:0.25 to 4.)
[Formula 16]

(In Chemical Formula 16,
R ₁₁ is hydrogen, a straight or branched C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C6 to C10 aryl group, a C1 to C12 carbonyl group, or a carboxyl group,
The molar ratio of b ₅ :a ₅ is 1:0.25 to 4.)
[Formula 17]

(In Chemical Formula 17,
R ₁₂ is a linear or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,
The molar ratio of b ₆ : a ₆ is 1:0.25 to 4.)
[Formula 18]

(In Chemical Formula 18,
R ₁₃ and R ₁₄ are each independently a straight or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,
The molar ratio of b ₇ :(a ₇ + a ₈ ) is 1:0.25 to 4.)
[Formula 19]

(In Chemical Formula 19,
R ₁₅ and R ₁₆ are each independently a straight or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,
The molar ratio of b ₈ :(a ₉ + a ₁₀ ) is 1:0.25 to 4.)
[Formula 20]

(In Chemical Formula 20,
R ₁₇ and R ₁₈ are each independently a straight or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,
The molar ratio of b ₉ :(a ₁₁ + a ₁₂ ) is 1:0.25 to 4.)
[Formula 21]

(In Chemical Formula 21,
R ₁₉ is hydrogen, a linear or branched C1 to C12 alkyl group, a C1 to C12 alkoxy group, a C6 to C10 aryl group, a C1 to C12 carbonyl group, or a carboxyl group,
R ₂₀ is a linear or branched C1 to C18 alkyl group, a C6 to C10 aryl group, or a C4 to C12 heterocyclic group including a hetero atom,
The molar ratio of b ₁₀ :(a ₁₃ + a ₁₄ ) is 1:0.25 to 4.) The method of claim 1,
The polymeric vinyl compound is a composition for cleaning a semiconductor substrate, characterized in that it is contained in an amount of 0.5 to 50% by weight, based on 100% by weight of the total composition comprising the same. The method of claim 1,
The organic solvent is a composition for cleaning a semiconductor substrate, characterized in that it is contained in an amount of 50 to 99.5% by weight, based on 100% by weight of the total composition containing the same. The method of claim 2,
The water-soluble monomolecular compound is a composition for cleaning a semiconductor substrate, characterized in that contained in an amount of 10 to 100 parts by weight, based on a total of 100 parts by weight of the polymeric vinyl compound. The method of claim 1,
The organic solvent is a composition for cleaning a semiconductor substrate, characterized in that it contains an organic solvent containing an -OH group in the molecule.