Composition of treatment agent for silicon substrate

Abstract

To provide a composition of a treatment agent for a silicon substrate according to an embodiment which has a low load at the time of an effluent treatment and can reduce the surface roughness (haze) of the surface of a silicon wafer.SOLUTION: The present disclosure relates to a composition of a treatment agent for a silicon substrate containing the following constituents A, B, and C in an embodiment: the constituent A is a cationic surface acting agent having at least one unsaturated bond and one of tertiary amino group and a quaternary ammonium group in a molecule; the constituent B is a soluble polymer: and the constituent C is polyethylene glycol.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a treating composition for silicon substrates and a method for using the same. [Background technology]

[0002] In recent years, the design rules for semiconductor devices have become finer due to the increasing demand for higher storage capacity of semiconductor memories. As a result, the depth of focus in photolithography used in the manufacturing process of semiconductor devices has become shallower, and the demand for reducing the surface roughness (haze) of silicon substrates (bare wafers) has become increasingly strict.

[0003] In order to improve the quality of silicon substrates, the silicon substrates are polished in multiple stages. In particular, the final polishing stage is performed to reduce haze. In addition, when a silicon substrate is polished using a polishing composition containing abrasive grains, the abrasive grains in the polishing composition usually adhere to the silicon substrate after polishing. In order to remove the adhered abrasive grains, the silicon substrate after polishing is generally rinsed with a rinse agent composition.

[0004] For example, Patent Document 1 proposes a chemical mechanical polishing composition containing an abrasive such as silica, a basic component such as ammonia, a compound such as a quaternary ammonium salt having 6 or more carbon atoms, and an aqueous carrier. The same document also proposes a rinse composition containing at least one compound selected from a quaternary polyammonium salt, a quaternary ammonium salt having 6 or more carbon atoms, and an alkylated polymer having an amide structure, and an aqueous carrier. Patent Document 2 describes a method for producing a water-soluble polymer comprising silica particles, a quaternary ammonium compound, and a water-soluble polymer, the quaternary ammonium compound having a quaternary ammonium group with a carbon number of 10 or more and 22 or less, and + A polishing liquid composition for silicon wafers has been proposed, in which the ratio b / a of the total number of moles b to the total number of moles a of silanol groups in silica particles is 0.005 or more and 2.00 or less. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2020-203980 A [Patent Document 2] JP 2018-107263 A Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, the requirements for the surface quality of polished silicon substrates have become increasingly stringent. Therefore, there is a demand for a treatment composition for silicon substrates, such as a polishing liquid composition or a rinse agent composition, which can further reduce the surface roughness (haze). On the other hand, with the improvement of semiconductor quality and the increase in demand, a large amount of processing agents is used in the production of silicon substrates, which has led to issues such as the environmental burden and increased costs of wastewater treatment.

[0007] Therefore, the present disclosure provides a treatment composition for silicon substrates that imposes a low environmental load during wastewater treatment and can reduce the surface roughness (haze) of silicon substrates, and a method for using the same. [Means for solving the problem]

[0008] In one aspect, the present disclosure relates to a treatment composition for silicon substrates, comprising the following component A, the following component B, and the following component C: Component A: A cationic surfactant having one or more unsaturated bonds and a tertiary amino group or a quaternary ammonium group in the molecule. Component B: Water-soluble polymer Component C: Polyethylene glycol

[0009] In one aspect, the present disclosure relates to a method for using a treatment composition supplied to the same polishing machine used for polishing, the method including supplying the treatment composition of the present disclosure to the polishing machine together with a polishing liquid composition containing silica particles and contacting it with a silicon substrate and a polishing pad, or supplying the treatment composition of the present disclosure to the polishing machine after the supply of the polishing liquid composition used for polishing to the polishing machine is stopped and contacting it with a silicon substrate and a polishing pad.

[0010] In one aspect, the present disclosure relates to a method for using a treating composition of the present disclosure as a rinse composition for silicon substrates.

[0011] In one aspect, the present disclosure relates to a method for using a treating composition of the present disclosure as a polishing composition for silicon substrates. Effect of the Invention

[0012] According to the present disclosure, it is possible to provide a treatment composition for silicon substrates that reduces the environmental load during wastewater treatment and that can reduce the surface roughness (haze) of silicon substrates, and a method for using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present disclosure is based on the finding that the use of a treatment composition containing a specific cationic surfactant, a nitrogen-containing basic compound, a water-soluble polymer, and polyethylene glycol in a rinsing treatment reduces the environmental impact during wastewater treatment and can reduce the surface roughness (haze) of a silicon substrate.

[0014] That is, in one aspect, the present disclosure relates to a treatment composition for silicon substrates (hereinafter also referred to as "treatment composition of the present disclosure") containing the following component A, the following component B, and the following component C: Component A: A cationic surfactant having one or more unsaturated bonds and a tertiary amino group or a quaternary ammonium group in the molecule. Component B: Water-soluble polymer Component C: Polyethylene glycol

[0015] According to one or more embodiments of the present disclosure, the environmental load during wastewater treatment is low, and the surface roughness (haze) of a silicon substrate can be reduced.

[0016] Although the details of the mechanism by which the effects of the present disclosure are exerted are not clear, it is presumed as follows. For example, a silicon wafer with a single crystal structure can be dissolved by hydroxy ions, but since there are dissolved and insoluble parts and the surface cannot be dissolved uniformly, it is presumed that the surface roughness (haze) worsens. The chemical structure of the insoluble parts is unknown, but since the dissolution reaction does not proceed with highly hydrophilic hydroxy ions, it is presumed that they have hydrophobic properties. In the present disclosure, a cationic surfactant (component A) having one or more unsaturated bonds and a tertiary amino group or a quaternary ammonium group in the molecule is used. The cationic surfactant (component A) is adsorbed to the hydrophobic insoluble portion on the silicon substrate, and the cationic portion (N + It is believed that either the cationic surfactant (component A) attracts the negatively charged hydroxyl ions, which act as a dissolving agent, and thus the dissolution proceeds, or that the cationic surfactant (component A) dissolves the material. As a result, the difference in the amount of dissolution between the dissolved and undissolved parts becomes smaller, and it is believed that the surface roughness (haze) can be reduced. Furthermore, it is considered that the etching reaction proceeds more because the hydrophobicity of the cationic surfactant increases and the amount of the cationic surfactant adsorbed to the hydrophobic insoluble portion increases. Therefore, it is considered that, as component A, a highly hydrophobic cationic surfactant having a long alkyl chain, such as a compound having a structure represented by formula (I) or (II), has a higher etching performance. As a result, it is considered that the difference in the amount of dissolution between the dissolved portion and the insoluble portion can be reduced, and the surface roughness (haze) can be reduced. On the other hand, it is known that highly hydrophobic cationic surfactants are difficult to decompose in the environment. However, it has been found that the cationic surfactant (component A) having an unsaturated bond and a tertiary amino group or a quaternary ammonium group in the present disclosure reduces surface roughness (haze) and has good biodegradability during wastewater treatment, thereby reducing the environmental burden during wastewater treatment. However, the present disclosure need not be construed as being limited to these mechanisms.

[0017] [Cationic surfactant (ingredient A)] The treatment composition of the present disclosure contains a cationic surfactant (hereinafter, also referred to as "Component A"). Component A is a cationic surfactant having one or more unsaturated bonds and a tertiary amino group or a quaternary ammonium group in the molecule. The unsaturated bonds include amide, ketone, and aldehyde. Component A may be one type or a combination of two or more types.

[0018] From the viewpoint of reducing surface roughness (haze), in one or more embodiments, component A is preferably a compound having a structure represented by the following formula (I) or the following formula (II). Component A may be used as a solid, or may be used in a liquid state (liquefied) from the viewpoint of handling. Examples of the liquefaction method include a method of reacting component A with hydrochloric acid and a method of diluting component A with a solvent such as isopropyl alcohol. In one or more embodiments, component A is preferably dissolved in the treatment composition, but a part of component A may be present in a solid state in the treatment composition. In one or more embodiments, component A in the treatment composition is a compound having a structure represented by the following formula (I), and in one or more other embodiments, is a mixture of a compound having a structure represented by the following formula (I) and a compound having a structure represented by the following formula (II). [ka]

[0019] In the formula (I), R 1 represents an alkyl group having 10 or more carbon atoms, and R 2 represents a hydrocarbon group having 1 to 3 carbon atoms, and R 3 are the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, -(CH2CH2O) n H (wherein n is 1 to 3) or a hydrogen atom; X - indicates a counter ion. In the formula (II), R 1 represents an alkyl group having 10 or more carbon atoms, and R 2 represents a hydrocarbon group having 1 to 3 carbon atoms, and R 3 are the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, -(CH2CH2O) n H (wherein n is 1 to 3) or a hydrogen atom. In the above formulas (I) and (II), R 1 From the viewpoint of reducing surface roughness (haze), R is preferably an alkyl group having 10 to 22 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms, and even more preferably an alkyl group having 16 to 22 carbon atoms. 2 From the viewpoint of reducing surface roughness (haze), R is preferably an alkyl group having 3 carbon atoms (propyl group). 3 From the viewpoint of reducing surface roughness (haze), the counter ion is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 carbon atom (methyl group) or a hydrogen atom. - ), hydrogen carbonate ion (HCO3 - ) etc.

[0020] Examples of component A include N-[3-(dimethylamino)propyl]docosanamide.

[0021] The content of component A in the treatment composition of the present disclosure is preferably 10 ppm or more, more preferably 20 ppm or more, and even more preferably 30 ppm or more from the viewpoint of reducing surface roughness (haze), and is preferably 150 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less from the viewpoint of improving biodegradability during wastewater treatment. More specifically, the content of component A in the treatment composition of the present disclosure is preferably 10 ppm or more and 150 ppm or less, more preferably 20 ppm or more and 100 ppm or less, and even more preferably 30 ppm or more and 50 ppm or less. When component A is a combination of two or more types, the content of component A refers to the total content thereof. In this disclosure, 10,000 ppm is 1 mass% (the same applies below).

[0022] [Water-soluble polymer (component B)] The treatment composition of the present disclosure contains a water-soluble polymer (hereinafter, also referred to as "component B"). From the viewpoint of imparting wettability, component B is preferably at least one water-soluble polymer selected from hydroxyalkyl cellulose and polyglycerin, and more preferably polyglycerin. The hydroxyalkyl cellulose may be at least one selected from hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, and hydroxybutyl cellulose. Component B may be one type or a combination of two or more types.

[0023] When component B is a hydroxyalkyl cellulose, the weight average molecular weight of component B is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 150,000 or more, from the viewpoint of reducing surface roughness (haze), and is preferably 500,000 or less, more preferably 400,000 or less, and even more preferably 300,000 or less. When component B is polyglycerol, from the same viewpoint, the weight average molecular weight of component B is preferably 2,000 or more, more preferably 2,500 or more, even more preferably 2,800 or more, and is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 6,000 or less. The weight average molecular weight of Component B can be measured by the method described in the Examples below.

[0024] The content of component B in the treatment composition of the present disclosure is preferably 10 ppm or more, more preferably 30 ppm or more, more preferably 50 ppm or more, and more preferably 100 ppm or more from the viewpoint of providing wettability, and is preferably 1,000 ppm or less, more preferably 500 ppm or less, more preferably 300 ppm or less, and more preferably 150 ppm or less from the viewpoint of improving biodegradability during wastewater treatment. More specifically, the content of component B in the treatment composition of the present disclosure is preferably 10 ppm or more and 1,000 ppm or less, more preferably 30 ppm or more and 500 ppm or less, more preferably 50 ppm or more and 300 ppm or less, and more preferably 100 ppm or more and 150 ppm or less. When component B is a combination of two or more types, the content of component B refers to the total content thereof.

[0025] The ratio B / A (mass ratio B / A) of the content of component B to the content of component A in the treatment composition of the present disclosure is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 2.0 or more from the viewpoint of reducing surface roughness (haze), and is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 2.0 or less from the viewpoint of improving biodegradability during wastewater treatment. More specifically, the mass ratio B / A in the treatment composition of the present disclosure is preferably 0.5 or more and 5.0 or less, more preferably 1.0 or more and 4.0 or less, and even more preferably 1.0 or more and 2.0 or less.

[0026] [Polyethylene glycol (component C)] The treatment composition of the present disclosure contains polyethylene glycol (hereinafter, also referred to as "component C").

[0027] The weight average molecular weight of component C is preferably 600 or more, more preferably 800 or more, and even more preferably 1000 or more from the viewpoint of reducing surface roughness (haze), and is preferably less than 10,000, more preferably 8,000 or less, and even more preferably 6,000 or less from the viewpoint of improving biodegradability during wastewater treatment. More specifically, the weight average molecular weight of component C is preferably 600 or more and less than 10,000, preferably 800 or more and 8,000 or less, and even more preferably 1,000 or more and 6,000 or less. The weight average molecular weight of component C can be measured by the method described in the examples below.

[0028] The content of component C in the treatment composition of the present disclosure is preferably 0.1 ppm or more, more preferably 1 ppm or more, more preferably 5 ppm or more, and more preferably 10 ppm or more from the viewpoint of reducing surface roughness (haze), and is preferably 1,000 ppm or less, more preferably 500 ppm or less, more preferably 100 ppm or less, more preferably 50 ppm or less, and more preferably 40 ppm or less from the viewpoint of improving biodegradability during wastewater treatment. More specifically, the content of component C in the treatment composition of the present disclosure is preferably 0.1 ppm or more and 1,000 ppm or less, more preferably 1 ppm or more and 500 ppm or less, more preferably 5 ppm or more and 100 ppm or less, more preferably 10 ppm or more and 50 ppm or less, and more preferably 10 ppm or more and 40 ppm or less. When component C is a combination of two or more types, the content of component C refers to the total content thereof.

[0029] The ratio C / A (mass ratio C / A) of the content of component C to the content of component A in the treatment composition of the present disclosure is preferably 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more from the viewpoint of improving biodegradability during wastewater treatment, and is preferably 2.0 or less, more preferably 1.5 or less, and even more preferably 1.0 or less from the viewpoint of reducing surface roughness (haze). From the same viewpoint, the mass ratio C / A in the treatment composition of the present disclosure is preferably 0.1 or more and 2.0 or less, more preferably 0.3 or more and 2.0 or less, and even more preferably 0.5 or more and 1.0 or less.

[0030] [water] In one or more embodiments, the treatment composition of the present disclosure may contain water. Examples of water include ion-exchanged water and ultrapure water, and ultrapure water is preferred from the viewpoint of reducing surface roughness (haze). The content of water in the treatment composition of the present disclosure may be, for example, the remainder of component A, component B, component C, and other components described below.

[0031] [Nitrogen-containing basic compound (component D)] The treatment composition of the present disclosure may further contain a nitrogen-containing basic compound (hereinafter, also referred to as "component D"). From the viewpoint of improving cleaning properties, component D is preferably a water-soluble nitrogen-containing basic compound. In the present disclosure, "water-soluble" refers to having a solubility of 0.5 g / 100 mL or more in water (20°C), preferably 2 g / 100 mL or more. In the present disclosure, "water-soluble nitrogen-containing basic" refers to a nitrogen-containing compound that exhibits basicity when dissolved in water. Component D does not include component A. Component D may be one type or a combination of two or more types.

[0032] In one or more embodiments, component D may be at least one selected from an amine compound and an ammonium compound. For example, component D may be one or a combination of two or more selected from ammonia, ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, dimethylamine, trimethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyl-N,N-diethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-(β-aminoethyl)ethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethylenediamine, hexamethylenediamine, piperazine hexahydrate, anhydrous piperazine, 1-(2-aminoethyl)piperazine, N-methylpiperazine, diethylenetriamine, tetramethylammonium hydroxide, and hydroxylamine. Among these, from the viewpoint of reducing surface roughness (haze), ammonia or a mixture of ammonia and hydroxyamine is preferred as component D, and ammonia is more preferred.

[0033] When the treatment composition of the present disclosure contains component D, the content of component D in the treatment composition of the present disclosure is preferably 5 ppm or more, more preferably 10 ppm or more, from the viewpoint of reducing surface roughness (haze) and improving cleaning properties, and from the same viewpoint, it is preferably 500 ppm or less, more preferably 300 ppm or less, more preferably 100 ppm or less, more preferably 50 ppm or less, more preferably 30 ppm or less, and more preferably 20 ppm or less. More specifically, the content of component D in the treatment composition of the present disclosure is preferably 5 ppm or more and 500 ppm or less, more preferably 10 ppm or more and 300 ppm or less, more preferably 10 ppm or more and 50 ppm or less, more preferably 10 ppm or more and 30 ppm or less, and more preferably 10 ppm or more and 20 ppm or less. When component D is a combination of two or more types, the content of component D refers to the total content thereof.

[0034] The ratio D / A (mass ratio D / A) of the content of component D to the content of component A in the treatment composition of the present disclosure is preferably 0.002 or more, more preferably 0.01 or more, and even more preferably 0.025 or more, from the viewpoints of reducing surface roughness (haze) and improving cleaning properties, and from the same viewpoints, is preferably 1 or less, more preferably 0.5 or less, and even more preferably 0.2 or less. More specifically, the mass ratio D / A in the treatment composition of the present disclosure is preferably 0.002 or more and 1 or less, more preferably 0.01 or more and 0.5 or less, and even more preferably 0.025 or more and 0.2 or less.

[0035] [Silica particles (component E)] In one or more embodiments, the treatment composition of the present disclosure may further contain silica particles (hereinafter also referred to as "component E") from the viewpoint of improving polishing performance. Examples of component E include colloidal silica, fumed silica, pulverized silica, and silica obtained by surface-modifying these, and from the viewpoint of reducing surface roughness (haze), colloidal silica is preferred. Component E may be one type or a combination of two or more types.

[0036] From the viewpoint of operability, the use form of component E is preferably a slurry form.When component E contained in the treatment composition of the present disclosure is colloidal silica, from the viewpoint of preventing contamination of silicon substrate by alkali metal, alkaline earth metal, etc., the colloidal silica is preferably obtained from the hydrolysis product of alkoxysilane.Silica particles obtained from the hydrolysis product of alkoxysilane can be prepared by a conventionally known method.

[0037] From the viewpoints of improving the polishing rate and reducing the surface roughness (haze), the average primary particle diameter of component E is preferably 10 nm or more, more preferably 15 nm or more, even more preferably 20 nm or more, and is preferably 40 nm or less, more preferably 35 nm or less, and even more preferably 30 nm or less. From the same viewpoint, the average primary particle diameter of component E is preferably 10 nm or more and 40 nm or less, more preferably 15 nm or more and 35 nm or less, and even more preferably 20 nm or more and 30 nm or less. In the present disclosure, the average primary particle diameter of component E is determined based on the specific surface area S (m 2 The specific surface area can be measured, for example, by the method described in the Examples.

[0038] From the viewpoints of improving the polishing rate and reducing the surface roughness (haze), the average secondary particle diameter of component E is preferably 20 nm or more, more preferably 30 nm or more, and even more preferably 40 nm or more, and from the same viewpoint, it is preferably 80 nm or less, more preferably 75 nm or less, and even more preferably 70 nm or less. More specifically, the average secondary particle diameter of component E is preferably 20 nm or more and 80 nm or less, more preferably 30 nm or more and 75 nm or less, and even more preferably 40 nm or more and 70 nm or less. In the present disclosure, the average secondary particle diameter is a value measured by a dynamic light scattering (DLS) method, and can be measured, for example, using the device described in the Examples.

[0039] From the viewpoints of improving the polishing rate and reducing the surface roughness (haze), the degree of association of component E is preferably 3 or less, more preferably 2.5 or less, and even more preferably 2.3 or less, and is preferably 1.1 or more, more preferably 1.5 or more, and even more preferably 1.8 or more. In the present disclosure, the degree of association of component E is a coefficient representing the shape of silica particles and is calculated by the following formula. Degree of association = average secondary particle size / average primary particle size

[0040] As a method for adjusting the degree of association of Component E, for example, the methods described in JP-A-6-254383, JP-A-11-214338, JP-A-11-60232, JP-A-2005-060217, JP-A-2005-060219, etc. can be used.

[0041] The shape of component E is preferably a so-called sphere type and / or a so-called cocoon type.

[0042] When the treatment composition of the present disclosure contains component E, the content of component E in the treatment composition of the present disclosure is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and even more preferably 0.07 mass% or more, calculated as SiO2, from the viewpoint of improving the polishing rate and reducing the surface roughness (haze), and from the same viewpoint, it is preferably 2.5 mass% or less, more preferably 1 mass% or less, even more preferably 0.5 mass% or less, and even more preferably 0.2 mass% or less. More specifically, the content of component E in the treatment composition of the present disclosure is preferably 0.01 mass% or more and 2.5 mass% or less, more preferably 0.05 mass% or more and 1 mass% or less, even more preferably 0.07 mass% or more and 0.5 mass% or less, and even more preferably 0.07 mass% or more and 0.2 mass% or less, calculated as SiO2. When component E is a combination of two or more kinds, the content of component E refers to the total content thereof.

[0043] [Other ingredients] The treatment composition of the present disclosure may further contain other components to the extent that the effects of the present disclosure are not impaired. In one or more embodiments, the other components include at least one selected from a pH adjuster other than Component D, a surfactant other than Component A, a water-soluble polymer other than Component B and Component C, a preservative, an alcohol, a chelating agent, and an oxidizing agent.

[0044] The pH of the treatment composition of the present disclosure is preferably 9 or more, more preferably 9.5 or more, and even more preferably 10 or more, from the viewpoint of reducing surface roughness (haze) and improving cleaning properties, and is preferably 12 or less, more preferably 11.5 or less, and even more preferably 11 or less, from the viewpoint of reducing surface roughness (haze). More specifically, the pH of the treatment composition of the present disclosure is preferably 9 or more and 12 or less, more preferably 9.5 or more and 11.5 or less, and even more preferably 10 or more and 11 or less. The pH of the treatment composition of the present disclosure can be adjusted using component D or a known pH adjuster. In the present disclosure, the above pH is the value of the treatment composition at 25°C and can be measured using a pH meter. The above pH can be, for example, a value measured by the method described in the Examples.

[0045] The treatment composition of the present disclosure can be produced, for example, by blending component A, component B, component C, and, if desired, optional components (component D, component E, and other components) by a known method. That is, in another aspect, the present disclosure relates to a method for producing a treatment composition, which includes a step of blending at least component A, component B, and component C. In the present disclosure, "blending" includes mixing component A, component B, component C, and optional components (component D, component E, and other components) simultaneously or in any order as necessary. The blending can be performed using, for example, a stirrer such as a homomixer, a homogenizer, an ultrasonic disperser, a wet ball mill, or a bead mill. The preferred blending amount of each component in the method for producing the treatment composition of the present disclosure can be the same as the preferred content of each component in the treatment composition of the present disclosure described above.

[0046] In the present disclosure, "the content of each component in the treatment composition" refers to the content of each component at the time of use, i.e., at the time when the treatment composition is started to be used for substrate treatment (e.g., polishing, rinsing treatment, etc.).

[0047] [Treatment composition concentrate] The treatment composition of the present disclosure may be produced as a concentrate from the viewpoint of storage and transportation, and may be diluted at the time of use. The concentration ratio is preferably 2 times or more, more preferably 10 times or more, even more preferably 30 times or more, even more preferably 50 times or more, from the viewpoint of production and transportation costs and storage stability, and is preferably 180 times or less, more preferably 140 times or less, even more preferably 100 times or less, even more preferably 70 times or less, from the viewpoint of storage stability. The treatment composition concentrate of the present disclosure can be used by diluting with water so that the content of each component at the time of use is the above-mentioned content (i.e., the content at the time of use). In the present disclosure, the "time of use" of the treatment composition concentrate refers to the state in which the treatment composition concentrate is diluted. When the treatment composition of the present disclosure is in the form of a concentrate, the content of Component A in the concentrate of the treatment composition of the present disclosure is preferably 0.1 mass % or more, more preferably 0.2 mass % or more, and even more preferably 0.3 mass % or more from the viewpoint of reducing surface roughness (haze), and is preferably 1.5 mass % or less, more preferably 1.0 mass % or less, and even more preferably 0.5 mass % or less, from the viewpoint of improving biodegradability during wastewater treatment. When the treatment composition of the present disclosure is in the form of a concentrate, the content of Component B in the concentrate of the treatment composition of the present disclosure is preferably 0.1 mass % or more, more preferably 0.3 mass % or more, and even more preferably 0.5 mass % or more, from the viewpoint of imparting wettability, and is preferably 10.0 mass % or less, more preferably 5.0 mass % or less, and even more preferably 3.0 mass % or less, from the viewpoint of improving biodegradability during wastewater treatment. When the treatment composition of the present disclosure is a concentrate, the content of component C in the concentrate of the treatment composition of the present disclosure is preferably 0.001% by mass or more, more preferably 0.010% by mass or more, and even more preferably 0.050% by mass or more, from the viewpoint of reducing surface roughness (haze), and is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and even more preferably 1.0% by mass or less, from the viewpoint of improving biodegradability during wastewater treatment. When the treatment composition of the present disclosure is a concentrate, the content of component D in the concentrate of the treatment composition of the present disclosure is, from the viewpoint of reducing surface roughness (haze) and improving cleaning ability, preferably 0.05 mass % or more, more preferably 0.10 mass % or more, and even more preferably 0.20 mass % or more, and from the viewpoint of reducing surface roughness (haze), preferably 3.00 mass % or less, more preferably 1.00 mass % or less, and even more preferably 0.50 mass % or less. When the treatment composition of the present disclosure is in the form of a concentrate, the content of Component E in the concentrate of the treatment composition of the present disclosure is preferably 1.0 mass % or more, more preferably 5.0 mass % or more, and even more preferably 7.0 mass % or more, from the viewpoint of improving the polishing rate and reducing the surface roughness (haze), and is preferably 25 mass % or less, more preferably 20 mass % or less, and even more preferably 10 mass % or less, from the viewpoint of product stability. When the treatment composition of the present disclosure is a concentrate, the pH of the concentrate of the treatment composition of the present disclosure is preferably 9.0 or more, more preferably 9.5 or more, and even more preferably 10.0 or more, from the viewpoint of reducing surface roughness (haze) and improving cleaning properties, and is preferably 13.0 or less, more preferably 12.5 or less, and even more preferably 12.0 or less, from the viewpoint of reducing surface roughness (haze). In the present disclosure, the above pH is the value of the concentrate of the treatment composition at 25°C, and can be measured using a pH meter. The above pH can be, for example, a value measured by the method described in the Examples.

[0048] [Method of using the treatment composition] In one or more embodiments, the treatment composition of the present disclosure can be used for rinsing a polished silicon substrate, as a dipping agent for a standby tank, as a cleaning agent used for dipping or with a PVA (polyvinyl alcohol) brush, etching, etc. That is, in one aspect, the present disclosure relates to a method for using the treatment composition of the present disclosure as a rinsing agent composition for silicon substrates. When the treatment composition of the present disclosure contains silica particles (component E), the treatment composition of the present disclosure can be used for polishing a silicon substrate in one or more embodiments. That is, the present disclosure relates to a method of using the treatment composition of the present disclosure as a polishing composition for silicon substrates in one aspect.

[0049] When the treatment composition of the present disclosure is used as a rinse composition for silicon substrates, in one or more embodiments, the treatment composition of the present disclosure is supplied to the same polishing machine as that used for polishing, and is used so as to come into contact with the silicon substrate and the polishing pad. In one or more embodiments, the treatment composition of the present disclosure may be supplied to the polishing machine together with a polishing liquid composition containing silica particles, or may be supplied to the polishing machine after the supply of the polishing liquid composition to the polishing machine is stopped. Therefore, in one aspect, the present disclosure relates to a method for using a treatment composition supplied to the same polishing machine as the polishing machine used for polishing, comprising: supplying the treatment composition of the present disclosure together with a polishing liquid composition containing silica particles to the polishing machine and contacting it with a silicon substrate and a polishing pad; or, after stopping the supply of the polishing liquid composition used for polishing to the polishing machine, contacting the treatment composition of the present disclosure with a silicon substrate and a polishing pad. Among these, a method for using the treatment composition of the present disclosure is preferred, comprising supplying the treatment composition of the present disclosure together with a polishing liquid composition containing silica particles to the polishing machine and contacting it with a silicon substrate and a polishing pad. According to the method for using the treatment composition of the present disclosure, the surface roughness (haze) of the silicon substrate can be reduced.

[0050] [Processing method] In one or a plurality of embodiments, the treatment composition of the present disclosure can be used for rinsing a silicon substrate that has been polished with a polishing composition containing silica particles. That is, in one aspect, the present disclosure relates to a treatment method for rinsing a silicon substrate polished with a polishing liquid composition containing silica particles, the treatment method comprising: supplying the treatment composition of the present disclosure together with the polishing liquid composition containing silica particles to a polishing machine and contacting the silicon substrate and polishing pad, or supplying the treatment composition of the present disclosure to the polishing machine after stopping the supply of the polishing liquid composition used for polishing to the polishing machine and contacting the silicon substrate and polishing pad (hereinafter also referred to as the "treatment method of the present disclosure"). The rinsing method in the treatment method of the present disclosure can be performed in the same manner as the rinsing step (2) in the semiconductor substrate manufacturing method of the present disclosure described below. According to the treatment method of the present disclosure, the surface roughness (haze) of the silicon substrate can be reduced.

[0051] [Method of manufacturing semiconductor substrate] In one or a plurality of embodiments, the treatment composition of the present disclosure is used in a rinsing step after a polishing step of a silicon substrate in the manufacturing process of a semiconductor substrate. That is, in one aspect, the present disclosure relates to a method for manufacturing a semiconductor substrate (hereinafter also referred to as the "semiconductor substrate manufacturing method of the present disclosure"), which includes the following steps (1), (2), and (3), and in which the following steps (1) and (2) are performed using the same polishing machine. (1) A polishing step of polishing a silicon substrate using a polishing composition containing silica particles. (2) A rinsing step in which the silicon substrate polished in step (1) (hereinafter also referred to as the "polished silicon substrate") is rinsed with the treatment composition of the present disclosure. (3) A cleaning step for cleaning the silicon substrate rinsed in step (2) (hereinafter also referred to as the "rinsed silicon substrate").

[0052] <Silicon substrate to be polished> Examples of the silicon substrate to be polished include single crystal 100-face silicon wafers, 111-face silicon wafers, 110-face silicon wafers, etc. From the viewpoint of reducing residues on the wafer surface, the resistivity of the silicon wafer is preferably 0.0001 Ω·cm or more, more preferably 0.001 Ω·cm or more, even more preferably 0.01 Ω·cm or more, even more preferably 0.1 Ω·cm or more, and is preferably 100 Ω·cm or less, more preferably 50 Ω·cm or less, even more preferably 20 Ω·cm or less. From a similar viewpoint, the resistivity of the silicon wafer is preferably 0.0001 Ω·cm or more and 100 Ω·cm or less, more preferably 0.001 Ω·cm or more and 100 Ω·cm or less, even more preferably 0.01 Ω·cm or more and 100 Ω·cm or less, even more preferably 0.1 Ω·cm or more and 100 Ω·cm or less, even more preferably 0.1 Ω·cm or more and 50 Ω·cm or less, and even more preferably 0.1 Ω·cm or more and 20 Ω·cm or less.

[0053] <Process (1): Polishing process> The polishing step includes a lapping (rough polishing) step of planarizing a silicon substrate obtained by slicing a silicon single crystal ingot into a thin disk shape, and a finish polishing step of etching the lapped silicon substrate and then mirror-finishing the silicon substrate surface. The treatment composition of the present disclosure is more preferably used in the rinsing step after the finish polishing step.

[0054] In the polishing step, for example, a polishing liquid composition is supplied between the silicon substrate to be polished and the polishing pad, and the polishing pad is moved relative to the silicon substrate to be polished while the silicon substrate to be polished and the polishing pad are in contact with each other. The polishing conditions, such as the type of polishing pad, the rotation speed of the polishing pad, the rotation speed of the substrate to be polished, the polishing load set in the polishing device equipped with the polishing pad, the supply speed of the polishing liquid composition, the polishing time, the temperature of the polishing liquid composition, and the surface temperature of the polishing pad, may be the same as the conventionally known polishing conditions, and can be appropriately set. The polishing load is, for example, 40 to 150 g / cm 2 The polishing load refers to the pressure of the platen applied to the surface of the silicon substrate to be polished during polishing. The polishing time is, for example, 100 to 600 seconds. The temperature of the polishing composition and the surface temperature of the polishing pad during polishing may be, for example, 15°C to 40°C.

[0055] In one or more embodiments, the polishing composition used in the polishing step contains silica particles as abrasive grains. Examples of silica particles include colloidal silica, fumed silica, pulverized silica, and silica obtained by surface modification of these. From the viewpoints of improving the polishing rate, reducing surface roughness (haze), and reducing surface defects (LPD) on the substrate surface, colloidal silica is preferred. The silica particles may be one type or a combination of two or more types. The content of silica particles in the polishing composition may be, for example, 0.05% by mass or more and 10% by mass or less. From the viewpoint of achieving an improvement in the polishing rate, a reduction in surface roughness (haze), and a reduction in surface defects (LPD), the polishing composition preferably contains a nonionic water-soluble polymer, more preferably a nonionic water-soluble polymer having an alkylene oxide group or a hydroxyl group in the molecule and a weight average molecular weight of 1,000 or more and less than 500,000. When the nonionic polymer has an alkylene oxide group in the molecule, examples of the alkylene oxide group include an ethylene oxide group and a propylene oxide group. From the viewpoint of achieving an improvement in the polishing rate, a reduction in surface roughness (haze), and a reduction in surface defects (LPD), examples of the nonionic polymer include at least one selected from polyglycerin, hydroxyalkyl cellulose, polyvinyl alcohol, and polyhydroxyethyl acrylamide. From the viewpoint of achieving both improved polishing rate and storage stability, the pH of the polishing composition is preferably greater than 8.5, more preferably 9 or more, even more preferably 9.5 or more, and even more preferably 10 or more, and from the viewpoint of improving surface quality, the pH is preferably 14 or less, more preferably 13 or less, even more preferably 12.5 or less, even more preferably 12 or less, even more preferably 11.5 or less, and even more preferably 11 or less. The polishing composition contains water as a medium, and the content of water in the polishing composition can be the balance of silica particles, the nonionic polymer, and optional components described below. In one or a plurality of embodiments, the polishing composition may contain optional components such as a water-soluble polymer, a basic compound, a pH adjuster, a preservative, an alcohol, and a chelating agent. In one or more other embodiments, the polishing composition used in the polishing step may be a treatment composition of the present disclosure containing silica particles (Component E).

[0056] <Step (2): Rinse step> In one or more embodiments, the rinse step can be performed by using the above-mentioned treatment method of the present disclosure.Therefore, in one or more embodiments, the rinse step includes: after step (1), without stopping the supply of the polishing liquid composition to the polishing machine, supplying the treatment composition of the present disclosure to the polishing machine together with the polishing liquid composition containing silica particles, and contacting the polished silicon substrate and polishing pad; or, after step (1), stopping the supply of the polishing liquid composition to the polishing machine, supplying the treatment composition of the present disclosure to the polishing machine, and contacting the treatment composition of the present disclosure to the polishing machine.

[0057] In the rinsing step, for example, the treatment composition of the present disclosure is supplied between the silicon substrate polished in step (1) (hereinafter also referred to as the "polished silicon substrate") and a polishing pad, and the polishing pad is moved relative to the polished silicon substrate while the polished silicon substrate and the polishing pad are in contact with each other.

[0058] The rinse treatment in the rinse step can be carried out using a polishing device used in the polishing step. The type of polishing pad, the rotation speed of the polishing pad, the rotation speed of the polished silicon substrate, the load set in the polishing device equipped with the polishing pad, the supply speed of the treatment composition (rinse agent composition), etc. may be the same as or different from the corresponding conditions in the polishing step. The rinse time is preferably 1 second or more, more preferably 3 seconds or more, from the viewpoint of suppressing adhesion of abrasive grains, and is preferably 60 seconds or less, more preferably 30 seconds or less, from the viewpoint of improving productivity. Here, the rinse time means the time during which the treatment composition (rinse agent composition) is supplied.

[0059] The polishing pad used in the rinsing step may be the same as the polishing pad used in the polishing step, and may be any type such as a nonwoven type or a suede type. The polishing pad used in the polishing step may be used in the rinsing step without being replaced, and in this case, the polishing pad may contain a small amount of abrasive grains of the polishing liquid composition. The rinsing step may also be performed on the silicon substrate that is still attached to the polishing device immediately after the polishing step.

[0060] The temperature of the treatment composition (rinse composition) used in the rinsing step may be, for example, 5 to 60°C.

[0061] The rinsing step is preferably carried out at least after the finish polishing step, but may be carried out after each of the rough polishing step and the finish polishing step.

[0062] The rinsing step may include a water rinse treatment using water as a rinse liquid before or after the rinsing treatment using the treatment composition (rinse composition) of the present disclosure. The time for the water rinse treatment is preferably 2 seconds or more and 30 seconds or less.

[0063] <Step (3): Cleaning step> In the cleaning step, for example, the silicon substrate rinsed in step (2) (hereinafter also referred to as "rinsed silicon substrate") is immersed in a cleaning agent, or the cleaning agent is sprayed onto the surface of the rinsed silicon substrate to be cleaned. Any conventionally known cleaning agent may be used as the cleaning agent, and examples of such cleaning agents include inorganic cleaning agents containing at least one selected from ozone, hydrogen peroxide, ammonia, hydrochloric acid, sulfuric acid, hydrofluoric acid, and ozone water. The cleaning time may be set depending on the cleaning method.

[0064] The semiconductor substrate manufacturing method of the present disclosure may further include a step of forming an element isolation film, a step of planarizing an interlayer insulating film, a step of forming metal wiring, and the like. EXAMPLES

[0065] The present disclosure will be described in more detail below with reference to examples, but these are merely illustrative and the present disclosure is not limited to these examples.

[0066] 1. Preparation of Treatment Composition (Rinse Composition) (Examples 1 to 5 and Comparative Examples 1 to 3) Each component shown in Table 1 and ultrapure water were mixed with stirring and adjusted to a pH of 10 at 25°C using a pH adjuster (ammonia) as necessary to prepare concentrates (concentration ratio: 20 times) of the treatment compositions of Examples 1 to 5 and Comparative Examples 1 to 3. The content of each component (ppm or mass %, active content) in Table 1 is the value for the treatment composition obtained by diluting the concentrate of the treatment composition 20 times. The content of ultrapure water is the remainder excluding component A or non-component A, component B, component C, component D, and component E. In Examples 1 to 5 and Comparative Examples 2 to 3 in Table 1, 51.8 g of ultrapure water, 48 g of 0.01 mol / L hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., for Volumetric Analysis), and 0.2 g of component A were mixed in this order and thoroughly stirred to liquefy component A, and the resulting mixture was blended to the content of component A shown in Table 1.

[0067] The following components A, non-component A, component B, component C, component D and component E were used in the preparation of each treatment composition. (Component A) N-[3-(dimethylamino)propyl]docosanamide [Kao Corporation, AMIDET APA-22] (Non-ingredient A) Hexadecyltrimethylammonium chloride [Tokyo Chemical Industry Co., Ltd.] (Component B) Polyglycerin [Daicel Corporation, XPW, degree of polymerization 40, weight average molecular weight 2,980] HEC: Hydroxyethyl cellulose [Daicel, SE-400, weight average molecular weight 250,000] (Component C) PEG 1000 [Polyethylene glycol, NOF Corp., PEG#1000, weight average molecular weight 1,000] (Component D) Ammonia [28% by weight ammonia water, Kishida Chemical Co., Ltd., special grade reagent] (Component E) Colloidal silica [average primary particle size 25 nm, average secondary particle size 49 nm, degree of association 2.0]

[0068] 2.Measuring methods for various parameters (1) Measurement of the average primary particle size of silica particles (component E) The average primary particle diameter (nm) of silica particles (component E) is calculated by the BET (nitrogen adsorption) method. 2 / g) using the following formula: Average primary particle diameter (nm)=2727 / S The specific surface area S of silica particles (component E) was measured by carrying out the following [pretreatment], and then weighing out approximately 0.1 g of a measurement sample into a measurement cell to four decimal places, drying the sample for 30 minutes in an atmosphere at 110°C immediately before measuring the specific surface area, and then measuring the specific surface area by the nitrogen adsorption method (BET method) using a specific surface area measuring device (Micromeritic automatic specific surface area measuring device "Flowsorb III2305", manufactured by Shimadzu Corporation). [Preprocessing] (a) The pH of a slurry of silica particles (component E) is adjusted to 2.5±0.1 with an aqueous nitric acid solution. (b) The slurry-like silica particles (component E) adjusted to a pH of 2.5±0.1 is placed in a petri dish and dried in a hot air dryer at 150°C for 1 hour. (c) After drying, the obtained sample is finely ground in an agate mortar. (d) The ground sample is suspended in ion-exchanged water at 40°C and filtered through a membrane filter with a pore size of 1 μm. (e) The residue on the filter is washed five times with 20 g of ion-exchanged water (40°C). (f) The filter with the filtrate attached thereto is placed in a petri dish and dried in an atmosphere at 110°C for 4 hours. (g) The dried filtrate (component E) was taken, being careful not to mix in any filter debris, and finely ground in a mortar to obtain a measurement sample.

[0069] (2) Average secondary particle size of silica particles (component E) The average secondary particle diameter (nm) of silica particles (component E) was measured by adding an abrasive to ion-exchanged water so that the concentration of component E was 0.25 mass%, and then placing the resulting aqueous dispersion in a disposable sizing cuvette (a 10 mm polystyrene cell) to a height of 10 mm from the bottom, using a dynamic light scattering method (apparatus name: Zetasizer Nano ZS, manufactured by Sysmex Corporation).

[0070] (3) Measurement of weight-average molecular weight of water-soluble polymers (component B, component C) The weight average molecular weight of the water-soluble polymers (component B, component C) was calculated based on the peaks in the chromatogram obtained by applying gel permeation chromatography (GPC) under the following conditions. <Measurement conditions> Equipment: HLC-8320 GPC (Tosoh Corporation, detector integrated) Column: α-M + α-M Eluent: 0.15 mol / L Na2SO4, 1% acetic acid by mass, solvent: water Flow rate: 1.0mL / min Column temperature: 40℃ Detector: Shodex RI SE-61 differential refractive index detector Standard: Pullulan with known molecular weight

[0071] (4) pH of the treatment composition The pH at 25° C. was measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and was the value measured one minute after immersing the electrodes of the pH meter in the treatment composition or a concentrate thereof.

[0072] 3. Treatment method (rinsing treatment) The prepared concentrate of the treating composition was diluted 20 times with ultrapure water to obtain a treating composition (pH 10), which was used to rinse the following silicon substrate (single-sided mirror-finished silicon wafer with a diameter of 200 mm, conductivity type: P, crystal orientation: 100, resistivity 0.1 Ω cm or more and less than 100 Ω cm) under the following rinsing conditions. Prior to the rinsing treatment, the silicon substrate was preliminarily coarsely polished using a commercially available polishing composition. Then, the finish polishing was performed under the following conditions, and immediately thereafter, the silicon substrate was rinsed under the following conditions using each treatment composition (rinse composition). The haze of the silicon substrate subjected to the finish polishing after the coarse polishing was 2-3 (ppm). The haze is a value measured using a dark field wide grazing incidence channel (DWO) using a KLA Tencor "Surfscan SP1-DLS". In Examples 1 to 5 and Comparative Examples 1 to 3, the polishing liquid composition was supplied for 150 seconds to carry out finish polishing, and then the treatment agent composition was supplied together with the polishing liquid composition for 30 seconds to carry out a rinsing treatment.

[0073] [Polishing compositions A and B used in final polishing] (Polishing liquid composition A) The polishing liquid composition A used for the final polishing was prepared by stirring and mixing silica particles ("PL-2" manufactured by Fuso Chemical Co., Ltd., average primary particle size 25 nm, average secondary particle size 49 nm, degree of association 2.0), polyglycerin (XPW manufactured by Daicel Corporation, weight average molecular weight 2,980), methyldiallylamine hydrochloride-sulfur dioxide copolymer (Nittobo Medical PAS-2201, weight average molecular weight 3,000), ammonia (manufactured by Kishida Chemical Co., Ltd., special grade reagent), and ion-exchanged water to prepare a concentrated solution. The concentrated solution was then diluted 100 times with ion-exchanged water immediately before use to obtain the polishing liquid composition A. The content of each component in the polishing liquid composition A was 0.1 mass% silica particles, 75 ppm methyldiallylamine hydrochloride-sulfur dioxide copolymer, 75 ppm polyglycerin, and 60 ppm ammonia. The pH of the polishing liquid composition A was 10. (Polishing liquid composition B) The polishing liquid composition B used for the finish polishing was prepared by stirring and mixing silica particles ("PL-2" manufactured by Fuso Chemical Co., Ltd., average primary particle diameter 25 nm, average secondary particle diameter 49 nm, degree of association 2.0), HEC (hydroxyethyl cellulose, "SE400" manufactured by Daicel Corporation, weight average molecular weight 250,000), PEG (polyethylene glycol, "PEG#6000" manufactured by NOF Corporation, weight average molecular weight 6,000), ammonia (manufactured by Kishida Chemical Co., Ltd., special grade reagent), and ion-exchanged water to prepare a concentrated solution. Then, the concentrated solution was diluted 20 times with ion-exchanged water immediately before use to obtain the polishing liquid composition B. The content of each component in the polishing liquid composition B was 0.1 mass% silica particles, 200 ppm HEC, 70 ppm ammonia, and 10 ppm PEG. The pH of the polishing liquid composition B was 10.

[0074] [Finishing polishing conditions] Grinding machine: Okamoto Kogyo's single-sided 8-inch grinding machine "GRIND-X SPP600s" Polishing pad: Toray Cortex suede pad (Asker hardness: 64, thickness: 1.37 mm, nap length: 450 μm, opening diameter: 60 μm) Load: 125g / cm 2 Plate rotation speed: 60 rpm Polishing time: 150 seconds Supply rate of polishing composition: 100 mL / min Temperature of the polishing composition: 23°C Carrier rotation speed: 62 rpm

[0075] [Rinse conditions] Polishing machine: The same polishing machine used for the finishing polishing Polishing pad: The same polishing pad used for the final polishing Load: 125g / cm 2 Plate rotation speed: 60 rpm Rinse time: 30 seconds Supply rate of treatment composition: 100 mL / min Temperature of treatment composition: 25°C Supply rate of polishing composition: 100 mL / min Temperature of the polishing composition: 23°C Carrier rotation speed: 62 rpm

[0076] 4. Cleaning method After the rinsing process, the silicon substrate was subjected to ozone cleaning and dilute hydrofluoric acid cleaning as follows. In the ozone cleaning, an aqueous solution containing 20 ppm ozone was sprayed from a nozzle at a flow rate of 1 L / min toward the center of the silicon substrate rotating at 600 rpm for 3 minutes. The temperature of the ozone water was kept at room temperature. Next, dilute hydrofluoric acid cleaning was performed. In the dilute hydrofluoric acid cleaning, an aqueous solution containing 0.5 mass% ammonium hydrogen fluoride (special grade: Nacalai Tesque, Inc.) was sprayed from a nozzle at a flow rate of 1 L / min toward the center of the silicon substrate rotating at 600 rpm for 6 seconds. The above ozone cleaning and dilute hydrofluoric acid cleaning were performed as one set, for a total of two sets, and finally spin drying was performed. In the spin drying, the silicon substrate was rotated at 1,500 rpm.

[0077] 5. Evaluation [Evaluation of surface roughness (haze) of silicon substrate] For the evaluation of the surface roughness (haze) of the silicon substrate after cleaning, the value (DWO haze) in the dark field wide oblique incidence channel (DWO) measured using the surface roughness measuring device "Surfscan SP1-DLS" (manufactured by KLA Tencor) was used. The smaller the numerical value of the DWO haze, the higher the surface smoothness. The measurement of the surface roughness (haze) was performed on two silicon substrates, and the average value was obtained. The results are shown in Table 1.

[0078] [BOD / COD] The biochemical oxygen demand (BOD) and the chemical oxygen demand (COD) were measured by the following measurement methods, and the BOD / COD ratio was calculated. The results are shown in Table 1. The higher the value of the BOD / COD ratio, the better the biodegradability. <COD measurement method> Measurement method: JIS K 1020 20.2 Test method for industrial wastewater - Method for measuring CODCr by spectrophotometry using a test tube with a lid Sample: The treatment agent composition was diluted 20 times with water for measurement. Absorbance device: DR2800 (manufactured by HACH) <BOD measurement method> Measurement method: Measured in accordance with JIS K 0102 21 and 32.3 Analytical method for biochemical oxygen demand (BOD) Sample: The treatment agent composition was diluted 1460 times with water for measurement. Seeding bacteria: Polyseed-US (manufactured by Consol Corporation)

[0079]

Table 1

[0080] As shown in Table 1, it was found that the treatment agent compositions of Examples 1 to 5 had a reduced surface roughness (haze) of the silicon substrate compared to Comparative Examples 1 to 3. In addition, since the treatment agent compositions of Examples 1 to 5 had a higher BOD / COD ratio value compared to Comparative Example 1, it was found that they were excellent in biodegradability and could reduce the environmental load during wastewater treatment. [Industrial Applicability]

[0081] The treatment composition of the present disclosure is useful as a rinse composition or a polishing composition used in the manufacturing process of various semiconductor substrates.

Claims

1. A treating agent composition for silicon substrates comprising the following component A, component B, and component C: Component A: a cationic surfactant having one or more unsaturated bonds and a tertiary amino group or a quaternary ammonium group in the molecule Component B: Water-soluble polymer Component C: Polyethylene glycol

2. 2. The treatment composition according to claim 1, wherein the unsaturated bond of component A is an amide, a ketone, or an aldehyde.

3. 3. The treatment composition according to claim 1, wherein Component A is a compound represented by the following formula (I) or (II): 【Chemical 1】 In the formula (I), R 1 represents an alkyl group having 10 to 22 carbon atoms, and R 2 represents a hydrocarbon group having 1 to 3 carbon atoms, and R 3 are the same or different and each represent a hydrocarbon group having 1 to 6 carbon atoms, -(CH 2 CH 2 O) n H (where n is 1 to 3) or a hydrogen atom, X - indicates a counter ion. In the formula (II), R 1 represents an alkyl group having 10 to 22 carbon atoms, and R 2 represents a hydrocarbon group having 1 to 3 carbon atoms, and R 3 are the same or different and each represent a hydrocarbon group having 1 to 6 carbon atoms, -(CH 2 CH 2 O) n H (where n is 1 to 3) or a hydrogen atom.

4. 3. The treatment composition according to claim 1, wherein the content of component A is 10 ppm or more and 100 ppm or less.

5. 3. The treatment composition according to claim 1, wherein component B is at least one water-soluble polymer selected from the group consisting of hydroxyalkyl cellulose and polyglycerin.

6. The treatment composition according to claim 1 or 2, further comprising a nitrogen-containing basic compound (component D).

7. The treatment composition according to claim 1 or 2, further comprising silica particles (component E).

8. A method for using a treatment composition supplied to the same polishing machine as that used for polishing, comprising:

3. Supplying the treatment composition according to claim 1 or 2 together with a polishing liquid composition containing silica particles to a polishing machine and contacting the silicon substrate and polishing pad, or 3. A method for using a treatment composition, comprising: after stopping the supply of a polishing liquid composition used for polishing to a polishing machine, supplying the treatment composition according to claim 1 or 2 to the polishing machine and contacting the composition with a silicon substrate and a polishing pad.

9. A method for using the treating composition according to claim 1 or 2 as a rinse composition for silicon substrates.

10. A method for using the treating composition according to claim 6 as an abrasive composition for silicon substrates.

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