Method for manufacturing a silicon substrate

Abstract

To provide a method for manufacturing silicon substrates, capable of reducing residues on a substrate surface.SOLUTION: According to one embodiment, the present disclosure relates to a method for manufacturing silicon substrates. The method includes: a step (1) of polishing a silicon substrate to be polished using a polishing liquid composition A; a step (2) of rinsing a polished silicon substrate using a rinse agent composition B; and a step (3) of cleaning a rinsed silicon substrate. The polishing liquid composition A in the step (1) includes silica particles a1, a water-soluble polymer a2, a nitrogen-containing basic compound a3, and an aqueous medium. The water-soluble polymer a2 is a water-soluble polymer containing an amino group or a quaternary ammonium group, and a pH of the polishing liquid composition A is 8 or more and 12 or less. The rinse agent composition B in the step (2) includes an anionic polymer b1, a hydrophilizing agent b2, and an aqueous medium. The anionic polymer b1 is an anionic polymer having a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group and at least one kind of an anionic group selected from these salts. The hydrophilizing agent b2 is at least one water-soluble polymer selected from among polyglycerin, a polyglycerin derivative, polyglycidol, and a polyglycidol derivative.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing a silicon substrate.

Background Art

[0002] In recent years, due to the increasing demand for higher recording capacities of semiconductor memories, the design rules of semiconductor devices have been continuously miniaturized. Therefore, in photolithography performed in the manufacturing process of semiconductor devices, the depth of focus has become shallower, and the requirements for reducing surface defects (LPD: Light point defects) and surface roughness (haze) of silicon substrates (bare wafers) have become increasingly strict.

[0003] For the purpose of improving the quality of silicon substrates, in the polishing process of polishing silicon wafers, there are a lapping (rough polishing) process for planarizing a silicon wafer obtained by slicing a silicon single crystal ingot into a thin disk shape, and a finishing polishing process for mirror-finishing the surface of the lapped silicon wafer after etching the lapped silicon wafer. In particular, the finishing polishing process performed at the final stage of polishing is carried out for the purpose of suppressing haze and reducing LPDs such as particles, scratches, and pits by improving the wettability (hydrophilicity) of the polished silicon substrate surface.

[0004] When a silicon substrate is polished using a polishing liquid composition containing abrasive grains, usually, particles derived from polishing debris, abrasive grains, etc. adhere to the polished silicon substrate. In order to remove the particles adhering to the substrate surface, it is generally performed to rinse the polished silicon substrate with a rinse agent composition. For example, in Patent Document 1, a method of rinsing using a rinse agent composition containing a nonionic polymer such as a polyglycerol derivative after polishing using a polishing liquid composition containing a nonionic polymer such as silica particles and HEC has been proposed. In Patent Document 2, a method has been proposed in which after polishing using an alkaline polishing liquid composition containing silica particles and a nonionic polymer such as polyglycerin, rinsing is performed using a rinsing agent composition containing a nonionic polymer such as polyglycerin. In Patent Document 3, a method has been proposed in which after polishing using an acidic polishing liquid composition containing sulfonic acid-modified colloidal silica, rinsing is performed using a rinsing agent composition containing an anionic polymer having an anionic group such as a sulfonic acid group. In Patent Document 4, a method has been proposed in which after polishing using an acidic polishing liquid composition containing ceria, rinsing is performed using a rinsing agent composition containing a vinyl polymer such as polyvinylacetamide, an anionic polymer, and a glycerin derivative.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0006] In polishing under alkaline conditions, both the silica particles derived from the polishing liquid and the surface charge of the silicon substrate to be polished are negatively charged. In order to improve the polishing rate, when a polishing liquid composition containing a polymer is used, the polymer contained in the polishing liquid composition adsorbs on the surfaces of both the silica particles and the silicon substrate to be polished, suppresses the electrostatic repulsion between the silicon substrate to be polished and the silica particles, and contributes to the improvement of the polishing rate. After performing such alkaline polishing, when using a rinsing agent containing a nonionic polymer as proposed in Patent Documents 1 and 2, it is possible to remove the particles remaining on the substrate surface by canceling the repulsion suppression between the silica particles and the silicon substrate to be polished. However, since the nonionic polymer derived from the abrasive (for example, HEC) is mixed during the rinsing process, there is a problem that it is difficult to suppress the reattachment of the silica particles to the substrate surface.

[0007] The present disclosure provides a method for manufacturing a silicon substrate capable of reducing residues on the substrate surface.

Means for Solving the Problems

[0008] In one aspect, the present disclosure includes a step (1) of polishing a silicon substrate to be polished using a polishing liquid composition A, a step (2) of rinsing the polished silicon substrate using a rinsing agent composition B, and a step (3) of cleaning the rinsed silicon substrate. The polishing liquid composition A in step (1) includes silica particles a1, a water-soluble polymer a2, a nitrogen-containing basic compound a3, and an aqueous medium. The water-soluble polymer a2 is a water-soluble polymer containing an amino group or a quaternary ammonium group, and the pH of the polishing liquid composition A is 8 or more and 12 or less. The rinsing agent composition B in step (2) includes an anionic polymer b1, a hydrophilizing agent b2, and an aqueous medium. The anionic polymer b1 is an anionic polymer having at least one anionic group selected from a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and salts thereof. The hydrophilizing agent b2 is at least one water-soluble polymer selected from polyglycerin, polyglycerin derivatives, polyglycidol, and polyglycidol derivatives. The present disclosure relates to a method for manufacturing a silicon substrate.

Effects of the Invention

[0009] According to the present disclosure, it is possible to provide a method for manufacturing a silicon substrate capable of reducing residues on the substrate surface.

Modes for Carrying Out the Invention

[0010] The present disclosure is based on the finding that by using a polishing liquid composition A containing silica particles a1, a water-soluble polymer a2 containing an amino group or a quaternary ammonium group, and a nitrogen-containing basic compound a3 in a polishing step, and using a rinsing agent composition containing a specific anionic polymer b1 and a specific hydrophilizing agent b2 in a rinsing step, the wettability of the substrate surface is improved and particles remaining on the substrate surface can be efficiently removed.

[0011] That is, in one aspect, the present disclosure provides a method for manufacturing a silicon substrate, comprising: a step (1) of polishing a silicon substrate to be polished using the polishing liquid composition A; a step (2) of rinsing the polished silicon substrate using the rinsing agent composition B; and a step (3) of cleaning the rinsed silicon substrate. The polishing liquid composition A in step (1) contains silica particles a1, a water-soluble polymer a2, a nitrogen-containing basic compound a3, and an aqueous medium. The water-soluble polymer a2 is a water-soluble polymer containing an amino group or a quaternary ammonium group. The pH of the polishing liquid composition A is 8 or more and 12 or less. The rinsing agent composition B in step (2) contains an anionic polymer b1, a hydrophilizing agent b2, and an aqueous medium. The anionic polymer b1 is an anionic polymer having at least one anionic group selected from a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and salts thereof. The hydrophilizing agent b2 is at least one water-soluble polymer selected from polyglycerin, polyglycerin derivatives, polyglycidol, and polyglycidol derivatives. The present disclosure relates to a method for manufacturing a silicon substrate (hereinafter, also referred to as "the method for manufacturing a silicon substrate of the present disclosure").

[0012] According to the present disclosure, in one or more embodiments, residues on the substrate surface can be reduced.

[0013] Although the detailed mechanism of the effect expression of the present disclosure is not clear, it is presumed as follows. In the polishing process of the present disclosure, by using a polishing liquid composition containing a water-soluble polymer a2 containing an amino group or a quaternary ammonium group, the surfaces of the silica particles a1 and the silicon substrate are covered with cationic groups derived from the water-soluble polymer a2, and during polishing, the original negative charges of the silica particles a1 and the silicon substrate are relaxed, making it easier for particles to stay at the polishing interface, and it is considered that efficient polishing can be achieved. In the rinsing process of the present disclosure, a specific anionic polymer b1 incorporated in the rinsing agent composition selectively acts on the cationic groups of the water-soluble polymer a2 derived from the polishing liquid composition by electrostatic interaction, so that during rinsing, the charge of the silicon substrate can be charged negatively, and it is considered that the reattachment of the silica particles a1 to the silicon substrate can be efficiently suppressed by the electrostatic repulsive force and the steric hindrance effect of the polymer. Furthermore, by incorporating a hydrophilic agent b2 into the rinsing agent composition, the surface of the wafer after rinsing is hydrophilically protected, and it is considered that particles remaining on the substrate surface can be more efficiently removed. However, the present disclosure may not be construed as being limited to these mechanisms.

[0014] In the present disclosure, "particle" refers to foreign matter remaining or adhering to the substrate surface. The "particles" in the present disclosure include foreign matter derived from polishing debris such as silicon oxide; foreign matter derived from polishing abrasive grains such as silicon oxide (silica); etc.

[0015] [Silicon substrate to be polished] Examples of the silicon substrate to be polished include, in one or more embodiments, a silicon substrate, etc., and in one or more embodiments, a single-crystalline silicon substrate, a polysilicon substrate, a substrate having a polysilicon film, a SiN substrate, etc. are included. From the viewpoint of exerting the effect of the polishing liquid composition of the present disclosure, a single-crystalline silicon substrate or a polysilicon substrate is preferable, and a single-crystalline silicon substrate is more preferable.

[0016] [Step (1): Polishing step] Step (1) in the method for manufacturing a silicon substrate of the present disclosure is a step of polishing a silicon substrate to be polished using a polishing liquid composition A (polishing step). In one or more embodiments, step (1) is preferably the final polishing step and / or the finishing polishing step. Note that the polishing liquid composition A used in step (1) (hereinafter also referred to as "the polishing liquid composition A of the present disclosure") will be described later.

[0017] Step (1) can include, for example, a lapping (rough polishing) step of planarizing a single-crystalline silicon substrate obtained by slicing a single-crystalline silicon ingot into a thin disk shape, and a finishing polishing step of mirror-finishing the surface of the lapped single-crystalline silicon substrate after etching the lapped single-crystalline silicon substrate. From the viewpoint of particle reduction, the polishing liquid composition A of the present disclosure is more preferably used in the finishing polishing step.

[0018] In step (1), for example, a polishing liquid composition is supplied between the silicon wafer to be polished and the polishing pad, and the polishing pad is relatively moved with respect to the silicon wafer to be polished while the silicon wafer to be polished and the polishing pad are in contact. The types of polishing pads used in step (1), the rotation speed of the polishing pad, the rotation speed of the substrate to be polished, the polishing load set in the polishing apparatus equipped with the polishing pad, the supply rate of the polishing liquid composition, the polishing time, the temperature of the polishing liquid composition, the surface temperature of the polishing pad, and other polishing conditions may be the same as the conventionally known polishing conditions and can be set as appropriate. As the polishing load, for example, 40~150 g / cm 2 can be mentioned. The polishing load refers to the pressure of the surface plate applied to the surface to be polished of the silicon substrate to be polished during polishing. As the polishing time, for example, 100~600 seconds can be mentioned. As the temperature of the polishing liquid composition and the surface temperature of the polishing pad during polishing, for example, 15°C~40°C can be mentioned.

[0019] [Step (2): Rinsing step] Step (2) is a step of rinsing the polished silicon substrate with the rinse agent composition B (rinsing step). Note that the rinse agent composition B used in step (2) (hereinafter also referred to as "the rinse agent composition B of the present disclosure") will be described later.

[0020] In step (2), for example, the rinse agent composition B of the present disclosure is supplied between the polished silicon substrate (hereinafter also referred to as "post-polishing silicon substrate") in step (1) and the polishing pad, and the polishing pad is relatively moved with respect to the post-polishing silicon substrate in a state where the post-polishing silicon substrate and the polishing pad are in contact with each other.

[0021] The rinsing process in step (2) can be carried out using the polishing apparatus used in the polishing process. The type of polishing pad used in step (2), the rotation speed of the polishing pad, the rotation speed of the post-polishing silicon wafer, the load set on the polishing apparatus equipped with the polishing pad, the supply rate of the rinse agent composition, etc. may be the same as or different from the corresponding conditions in the polishing process. From the viewpoint of suppressing the adhesion of abrasive grains, the rinsing time is preferably 1 second or more, more preferably 3 seconds or more, and from the viewpoint of improving productivity, it is preferably 60 seconds or less, more preferably 30 seconds or less. Here, the rinsing time means the time during which the rinse agent composition is being supplied. The polishing pad used in step (2) may be the same as the polishing pad used in the polishing process, and may be of any type such as a non-woven fabric type or a suede type. Also, the polishing pad used in the polishing process may be used in the rinsing process as it is without replacement. In this case, the abrasive grains of the polishing liquid composition may be slightly contained in the polishing pad. The rinsing process can also be carried out on the silicon substrate still attached to the polishing apparatus immediately after the polishing process. Examples of the temperature of the rinse agent composition B used in step (2) include 5 to 60°C.

[0022] Step (2) 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.

[0023] Step (2) may include a water rinsing process using water as the rinsing liquid before and after the rinsing process performed using the oral rinse composition B of the present disclosure. The water rinsing time is preferably 2 seconds or more and 30 seconds or less.

[0024] [Step (3): Cleaning Step] Step (3) is a step (cleaning step) of cleaning the silicon substrate rinsed in step (2) (hereinafter also referred to as "rinsed silicon substrate"). In step (3), from the viewpoint of reducing residues on the surface of the silicon substrate, it is preferable to perform inorganic cleaning. Examples of the cleaning agent used in inorganic cleaning include inorganic cleaning agents containing at least one selected from hydrogen peroxide, ammonia, hydrochloric acid, sulfuric acid, hydrofluoric acid, and ozone water. Examples of the cleaning method in step (3) include a method of immersing the rinsed silicon substrate in the cleaning agent and a method of injecting the cleaning agent onto the surface to be cleaned of the rinsed silicon substrate.

[0025] In one or more embodiments, the method for manufacturing a silicon substrate of the present disclosure may further include a step of rinsing the cleaned silicon substrate with water and drying it after the cleaning step.

[0026] [Polishing Liquid Composition A] In one or more embodiments, the polishing liquid composition A used in step (1) includes silica particles a1, a water-soluble polymer a2, a nitrogen-containing basic compound a3, and an aqueous medium.

[0027] [Silica Particles a1 (Component a1)] Examples of the silica particles (hereinafter also referred to as "component a1") contained in the polishing liquid composition A of the present disclosure include colloidal silica, fumed silica, pulverized silica, or silica obtained by surface-modifying them. From the viewpoints of improving the polishing rate, reducing residues on the substrate surface, and improving surface quality such as reducing surface roughness (haze), surface defects, and scratches, colloidal silica is preferable. Component a1 may be one type or a combination of two or more types.

[0028] As the usage form of component a1, a slurry form is preferable from the viewpoint of operability. When component a1 contained in the polishing liquid composition of the present disclosure is colloidal silica, from the viewpoint of preventing contamination of the silicon substrate by alkali metals, alkaline earth metals, etc., the colloidal silica is preferably obtained from a hydrolyzate of alkoxysilane. Silica particles obtained from a hydrolyzate of alkoxysilane can be produced by a conventionally known method.

[0029] From the viewpoint of improving the polishing rate, the average primary particle diameter of component a1 is preferably 10 nm or more, more preferably 15 nm or more, still more preferably 20 nm or more, and from the viewpoint of reducing the surface roughness of the substrate, it is preferably 50 nm or less, more preferably 45 nm or less, still more preferably 40 nm or less, and still more preferably 30 nm or less. More specifically, the average primary particle diameter of component a1 is preferably 10 nm or more and 50 nm or less, more preferably 15 nm or more and 45 nm or less, still more preferably 20 nm or more and 40 nm or less, and preferably 20 nm or more and 30 nm or less. In the present disclosure, the average primary particle diameter of component a1 is calculated using the specific surface area S (m 2 / g) calculated by the nitrogen adsorption method (BET method). The value of the average primary particle diameter is the value measured by the method described in the examples.

[0030] From the viewpoint of improving the polishing rate, the average secondary particle diameter of component a1 is preferably 20 nm or more, more preferably 30 nm or more, still more preferably 40 nm or more, and from the viewpoint of reducing the surface roughness of the substrate, it is preferably 100 nm or less, more preferably 90 nm or less, still more preferably 80 nm or less, still more preferably 70 nm or less, and still more preferably 60 nm or less. More specifically, the average secondary particle diameter of component a1 is preferably 20 nm or more and 100 nm or less, more preferably 30 nm or more and 90 nm or less, still more preferably 30 nm or more and 80 nm or less, still more preferably 30 nm or more and 70 nm or less, and still more preferably 40 nm or more and 60 nm or less. In the present disclosure, the average secondary particle diameter is a value measured by the dynamic light scattering (DLS) method, and is the value measured by the method described in the examples.

[0031] From the perspective of reducing the surface roughness of the substrate, the degree of aggregation of Component A1 is preferably 3 or less, more preferably 2.5 or less, still more preferably 2.3 or less. From the perspectives of improving the polishing rate and surface quality, it is preferably 1.1 or more, more preferably 1.5 or more, and still more preferably 1.8 or more. In the present disclosure, the degree of aggregation of Component A1 is a coefficient representing the shape of silica particles and is calculated by the following formula. Degree of aggregation = average secondary particle diameter / average primary particle diameter

[0032] As a method for adjusting the degree of aggregation of Component A1, 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 adopted.

[0033] From the perspective of improving the polishing rate, the content of Component A1 in the polishing liquid composition A of the present disclosure is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and still more preferably 0.03% by mass or more in terms of SiO2 conversion. From the perspective of particle removability, it is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.1% by mass or less. More specifically, the content of Component A1 in the polishing liquid composition A of the present disclosure is preferably 0.01% by mass or more and 0.5% by mass or less, more preferably 0.02% by mass or more and 0.2% by mass or less, and still more preferably 0.03% by mass or more and 0.1% by mass or less. When Component A1 is a combination of two or more types, the content of Component A1 refers to their total content.

[0034] <Water-soluble polymer A2 (Component A2) containing an amino group or a quaternary ammonium group> The water-soluble polymer A2 (hereinafter also referred to as "Component A2") contained in the polishing liquid composition A of the present disclosure is a water-soluble polymer containing an amino group or a quaternary ammonium group. In the present disclosure, "water-soluble" means having a solubility of 0.5 g / 100 mL or more, preferably 2 g / 100 mL or more, in water (20°C).

[0035] As component a2, in one or more embodiments, water-soluble polymers containing amino groups can be mentioned. From the viewpoints of improving the polishing rate and reducing residues on the substrate surface, it is preferable that the water-soluble polymer containing amino groups contains structural units derived from one or more monomers selected from allylamine and diallylamine. From the viewpoint of availability, in one or more embodiments, it is preferable that component a2 is a water-soluble polymer containing amino groups containing structural units derived from allylamine (hereinafter, also referred to as "component a2-1"), and in one or more embodiments, it is preferable that component a2 is a water-soluble polymer containing amino groups containing structural units derived from diallylamine (hereinafter, also referred to as "component a2-2"). As component a2, in one or more embodiments, from the viewpoints of improving the polishing rate and reducing residues on the substrate surface, polyvinyl alcohol having an amino group or a quaternary ammonium group (hereinafter, also referred to as "component a2-3") can be mentioned.

[0036] (Component a2-1: Amino group-containing water-soluble polymer containing structural units derived from allylamine) In one or more embodiments, at least a part of the amino groups in the structural units derived from allylamine preferably has a steric shielding group from the viewpoints of improving the polishing rate, storage stability of the polishing liquid, and reducing residues on the substrate surface. In the present disclosure, the steric shielding group refers to a steric (bulky) substituent that can shield the nitrogen atom of the amino group of component a2-1 to suppress cationization, that is, lower the pKa. From the same viewpoints, the amino group having the steric shielding group is preferably a secondary amino group or a tertiary amino group containing a hydrocarbon group having 3 to 11 carbon atoms and having a hydroxyl group. The number of carbon atoms of the hydrocarbon group is preferably 3 or more from the viewpoints of improving the shielding property of the amino group (suppressing the cationization of the nitrogen atom of the amino group), improving the polishing rate, and reducing residues on the substrate surface, and preferably 11 or less, more preferably 7 or less, still more preferably 5 or less, and still more preferably 4 or less from the viewpoints of improving water solubility and availability.

[0037] The amino group having the steric shielding group is, in one or more embodiments, a modifying group of the amino group with a glycidol derivative, and in one or more embodiments, is a group formed by the reaction of the amino group in the structural unit derived from allylamine and the glycidol derivative. At least a part of the total amino groups of component a2-1 is modified with a glycidol derivative to become an amino group having a steric shielding group. The equivalent amount of the glycidol derivative with respect to the number of amino groups (1 equivalent) in the structural unit derived from allylamine (hereinafter, also referred to as "glycidol modification rate") is preferably 0.3 or more, more preferably 0.5 or more, further preferably 0.8 or more, still further preferably 1 or more, preferably more than 1.1, more preferably 1.2 or more, still further preferably 1.3 or more, still further preferably 1.4 or more, still further preferably 1.5 or more, from the viewpoint of improving the surface quality, and preferably 4 or less, more preferably 3 or less, still further preferably 2.5 or less, still further preferably 2 or less, still further preferably 1.9 or less, still further preferably 1.6 or less, from the viewpoint of improving the polishing rate.

[0038] In the present disclosure, the glycidol modification rate is 13 a value measured by the method described in the examples using 13C-NMR. However, the glycidol modification rate can also be measured by the following method (1) or (2). (1) It can be determined from the amino group equivalent of the allylamine polymer used as the reaction raw material and the number of moles of the glycidol derivative. (2) Measure the nitrogen content N (mass%) of the reaction product of the glycidol derivative and the allylamine polymer, and it can be determined from the following formula. Glycidol modification rate = A / B Here, A = (100 - N × molecular weight of allylamine monomer / 14) / molecular weight of glycidol derivative, and B = N / 14.

[0039] Examples of the glycidol derivative include glycidol, alkyl glycidyl ether, etc. From the viewpoints of availability and improvement of polishing rate, glycidol is preferred. From the viewpoint of availability, the alkyl group of the alkyl glycidyl ether preferably has 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a 2-ethylhexyl group. Examples of the alkyl glycidyl ether include methyl glycidyl ether and 2-ethylhexyl glycidyl ether.

[0040] In one or more embodiments, Component a2-1 includes polyallylamine in which at least some amino groups have a steric shielding group, and in one or more embodiments, includes a reaction product of polyallylamine and a glycidol derivative.

[0041] In one or more embodiments, Component a2-1 includes a compound (glycidol-modified polyallylamine) containing a structural unit of the following formula (I). [Chemical formula]

[0042] In formula (I), R 1 and R 2 are each a hydrogen atom or a steric shielding group. Examples of the steric shielding group include a modifying group derived from a glycidol derivative. In one or more embodiments, examples thereof include a 1-molar adduct or a 2-molar adduct of glycidol, and in one or more embodiments, -CH2CH(OH)CH2(OH), -CH2CH(OH)CH2O-CH2CH(OH)CH2(OH), etc.

[0043] (Component a2-2: Amino group-containing water-soluble polymer containing a structural unit derived from diallylamine) In at least a part of the amino groups in the structural units derived from diallylamine, in one or more embodiments, from the viewpoints of improving the polishing rate, storage stability of the polishing liquid, and reducing residues on the substrate surface, it is preferable to have an electron-withdrawing group at the β-position or γ-position of the amino group. Examples of the electron-withdrawing group include a group represented by the following formula (II).

[0044]

Chemical formula

[0045] As component a2-2, in one or more embodiments, compounds containing structural units derived from diallylamine and structural units derived from sulfur dioxide are included. For example, compounds containing structural units represented by the following formula (III) are included.

Chemical formula

[0046] In formula (III), R 3 is an alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group. From the viewpoints of availability and economy, R 3 is preferably a methyl group. Also, n + m = 1, and n and m are 0 or 1. From the same viewpoints, compounds with m = 1 and n = 0 are preferable. Note that a mixture of a compound with m = 1 and n = 0 and a compound with m = 0 and n = 1 may also be used.

[0047] As component a2-2, in one or more embodiments, compounds containing structural units represented by the following formula (IV) are included. For example, a methyldiallylamine / sulfur dioxide copolymer is included.

Chemical formula

[0048] (Component a2-3: Polyvinyl alcohol having an amino group or a quaternary ammonium group) Component a2-3 is, in one or more embodiments, a compound having a structural unit (a31) represented by the following formula (IX-1), a structural unit (a32) represented by the following formula (IX-2), and a structural unit (a33) represented by the following formula (IX-3) (hereinafter also referred to as "cationized polyvinyl alcohol").

Chemical formula

[0049] In the above formula (IX-2), R is an alkyl group having 1 to 3 carbon atoms. In formula (IX-3), X 3 is a structural unit derived from an unsaturated compound having a cationic group (amino group or quaternary ammonium group) in the molecule and copolymerizable with a vinyl alcohol lower fatty acid ester.

[0050] The cationized polyvinyl alcohol having the structural unit (a31), the structural unit (a32), and the structural unit (a33) is obtained by copolymerizing the monomer compound that is the source of the structural unit (a32) and the monomer compound that is the source of the structural unit (a33), and then partially saponifying the obtained copolymer. For example, when R in formula (IX-2) is a methyl group, the cationized polyvinyl alcohol obtained by partially saponifying a copolymer of a polymerizable cation monomer (the compound that is the source of the structural unit (a33)) and vinyl acetate can be used as the above-mentioned polymer compound having a cationic group.

[0051] Here, the constitutional unit (a33) contains a cationic group (amino group or quaternary ammonium group), and the monomer compound that is the source of the constitutional unit (a33) is a compound copolymerizable with a vinyl alcohol lower (C1-C3) fatty acid ester (the monomer compound that is the source of the constitutional units (a31) and (a32)). Examples of the monomer compound that is the source of the constitutional unit (a33) include compounds selected from the compound represented by the following formula (X-1) and the compound represented by the following formula (X-2). From the viewpoint of improving the filtration throughput, it is preferable that the constitutional unit (a33) is derived from at least one compound selected from the compound represented by the following (X-1) and the compound represented by the following formula (X-2). [Chemical formula]

[0052] In formula (X-1) and formula (X-2), R 21 , R 22 , R 23 , R 27 , R 28 , R 29 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Y 3 , Y 4 are each independently an alkylene group having 1 to 12 carbon atoms, -COOR 32 -, -CONHR 32 -, -OCOR 32 -, and R 33 -OCO-R 32 -. Here, R 32 , R 33 are each independently an alkylene group having 1 to 5 carbon atoms. R 24 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or R 21 R 22 C=C(R 23 )-Y 3 -. R 25 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and R 26is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group, and Z - represents an anion. R 30 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or R 27 R 28 C=C(R 29 )-Y 4 -. R 31 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. Z - is, for example, a halogen ion.

[0053] Examples of the monomer compound that is a source of the structural unit (a33) include diallyldialkyl (the alkyl group has 1 to 3 carbon atoms) ammonium salts, N-(meth)acryloylaminoalkyl (the alkyl group has 1 to 5 carbon atoms)-N,N-dialkyl (the alkyl group has 1 to 3 carbon atoms) amines, N-(meth)acryloylaminoalkyl (the alkyl group has 1 to 5 carbon atoms)-N,N,N-trialkyl (the alkyl group has 1 to 3 carbon atoms) ammonium salts, N-(meth)acryloyloxyalkyl (the alkyl group has 1 to 5 carbon atoms)-N,N,N-trialkyl (the alkyl group has 1 to 3 carbon atoms) ammonium salts, and N-(ω-alkenyl (the alkenyl group has 2 to 10 carbon atoms))-N,N-dialkyl (the alkyl group has 1 to 3 carbon atoms) amines.

[0054] Component a2-3 may contain other structural units in addition to the structural units (a31) to (a33) as long as the effects of the present disclosure are not impaired, but it is preferably substantially free of them, and more preferably free of them.

[0055] In all the structural units of component a2-3, the molar concentrations of the structural unit (a31), the structural unit (a32), and the structural unit (a33) are preferably 50 to 100 mol%, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%, even more preferably substantially 100 mol%, and even more preferably 100 mol% from the viewpoint of improving the filter throughput.

[0056] From the viewpoint of improving the filter liquid passing rate, the molar concentration of the constitutional unit (a33) in all the constitutional units of component a2-3 is 0.001 mol% or more, preferably 0.01 mol% or more, more preferably 0.05 mol% or more, still more preferably 0.10 mol% or more, and even more preferably 0.20 mol% or more. Also, from the viewpoint of improving the filter liquid passing rate, the molar concentration of the constitutional unit (a33) is 1.5 mol% or less, preferably 1 mol% or less, more preferably 0.35 mol% or less, still more preferably 0.25 mol% or less. Therefore, from the viewpoint of improving the filter liquid passing rate, the molar concentration of the constitutional unit (a33) in all the constitutional units of component a2-3 is 0.001 to 1.5 mol%, preferably 0.01 to 1 mol%, more preferably 0.05 to 1 mol%, still more preferably 0.10 to 0.35 mol%, even more preferably 0.20 to 0.35 mol%, and even more preferably 0.20 to 0.25 mol%. Here, the molar concentration of the constitutional unit (a33) can be measured by the [Method for Measuring Cationization Modification Rate] described in the examples.

[0057] In one or more embodiments, examples of component a2-3 include a compound (cationized polyvinyl alcohol) containing a constitutional unit represented by the following formula (XI).

Chemical formula

[0058] From the viewpoints of improving the polishing rate and reducing residues on the substrate surface, the weight average molecular weight of component a2 is preferably 800 or more, more preferably 1,000 or more, still more preferably 1,500 or more, and even more preferably 2,000 or more. From the viewpoints of the storage stability of the polishing liquid and reducing residues on the substrate surface, the weight average molecular weight is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, even more preferably 20,000 or less, still more preferably 15,000 or less, and even more preferably 12,000 or less. The weight average molecular weight of component B in the present disclosure can be measured, for example, by the method described in the examples. When component a2 is component a2-1, from the viewpoints of improving the polishing rate and reducing residues on the substrate surface, the weight-average molecular weight of component a2 is preferably 800 or more, more preferably 1,000 or more, still more preferably 1,500 or more, still more preferably 2,000 or more, preferably 3,000 or more, more preferably 5,000 or more, still more preferably 6,000 or more, still more preferably 7,000 or more, and from the viewpoints of the storage stability of the polishing liquid and reducing residues on the substrate surface, it is preferably 100,000 or less, more preferably 55,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less. When component a2 is component a2-2, from the viewpoints of improving the polishing rate and reducing residues on the substrate surface, the weight-average molecular weight of component a2 is preferably 800 or more, more preferably 1,000 or more, still more preferably 1,500 or more, still more preferably 2,000 or more, and from the viewpoints of the storage stability of the polishing liquid and reducing residues on the substrate surface, it is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, still more preferably 20,000 or less, still more preferably 15,000 or less, still more preferably 12,000 or less, still more preferably 10,000 or less, still more preferably 7,000 or less, still more preferably 5,000 or less, still more preferably 4,000 or less. When component a2 is component a2-3, from the viewpoints of improving the polishing rate and reducing residues on the substrate surface, the weight-average molecular weight of component a2 is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 30,000 or more, and from the viewpoints of the storage stability of the polishing liquid and reducing residues on the substrate surface, it is preferably 100,000 or less, more preferably 90,000 or less, still more preferably 85,000 or less.

[0059] From the viewpoints of improving the polishing rate and reducing residues on the substrate surface, the content of component a2 in the polishing liquid composition A of the present disclosure is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, still more preferably 0.003% by mass or more. From the viewpoints of the storage stability of the polishing liquid and reducing residues on the substrate surface, the content is preferably 0.05% by mass or less, more preferably 0.02% by mass or less, still more preferably 0.01% by mass or less. More specifically, the content of component a2 in the polishing liquid composition A of the present disclosure is preferably 0.001% by mass or more and 0.05% by mass or less, more preferably 0.002% by mass or more and 0.02% by mass or less, still more preferably 0.003% by mass or more and 0.01% by mass or less. When component a2 is a combination of two or more kinds, the content of component a2 refers to their total content.

[0060] <Nitrogen-containing basic compound a3 (component a3)> The nitrogen-containing basic compound a3 (hereinafter also referred to as "component a3") contained in the polishing liquid composition A of the present disclosure is preferably a water-soluble nitrogen-containing basic compound from the viewpoints of improving the polishing rate, reducing residues on the substrate surface, and improving the surface quality. In the present disclosure, "water-soluble nitrogen-containing basic" refers to a nitrogen-containing compound that exhibits basicity when dissolved in water. In one or more embodiments, component a2 is not included in component a3. Component a3 may be one kind or a combination of two or more kinds.

[0061] As component a3, in one or more embodiments, at least one selected from amine compounds and ammonium compounds can be mentioned. Examples of component a3 include, for example, ammonia, ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, dimethylamine, trimethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, N-methyl ethanolamine, N-methyl-N,N-diethanolamine, N,N-dimethyl ethanolamine, N,N-diethyl ethanolamine, N,N-dibutyl ethanolamine, N-(β-aminoethyl) ethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethylenediamine, hexamethylenediamine, piperazine hexahydrate, anhydrous piperazine, 1-(2-aminoethyl) piperazine, N-methyl piperazine, diethylenetriamine, tetramethylammonium hydroxide, and hydroxylamine, and one or a combination of two or more thereof can be mentioned. Among these, from the viewpoint of reducing residues on the substrate surface, as component a3, ammonia or a mixture of ammonia and hydroxylamine is preferable, and ammonia is more preferable.

[0062] From the viewpoint of improving the polishing rate and the storage stability of the polishing liquid, the content of component a3 in the polishing liquid composition A of the present disclosure is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.002% by mass or more, and from the viewpoint of reducing residues on the substrate surface, it is preferably 0.05% by mass or less, more preferably 0.03% by mass or less, still more preferably 0.015% by mass or less, and still more preferably 0.01% by mass or less. More specifically, the content of component a3 in the polishing liquid composition A of the present disclosure is preferably 0.0005% by mass or more and 0.05% by mass or less, more preferably 0.001% by mass or more and 0.03% by mass or less, still more preferably 0.002% by mass or more and 0.015% by mass or less, and still more preferably 0.002% by mass or more and 0.01% by mass or less. When component a3 is a combination of two or more, the content of component a3 refers to their total content.

[0063] <aqueous medium> Examples of the aqueous medium contained in the polishing liquid composition A of the present disclosure include water such as distilled water, ion-exchanged water, pure water, and ultrapure water, or a mixed solvent of water and a solvent. Examples of the solvent include a solvent miscible with water (for example, an alcohol such as ethanol). When the aqueous medium is a mixed solvent of water and a solvent, the ratio of water to the entire mixed medium may not be particularly limited as long as the effects of the present disclosure are not hindered. From the viewpoint of economy, for example, 95% by mass or more is preferable, 98% by mass or more is more preferable, and substantially 100% by mass is even more preferable. From the viewpoint of reducing residues on the substrate surface, water is preferable as the aqueous medium, ion-exchanged water and ultrapure water are more preferable, and ultrapure water is even more preferable. The content of the aqueous medium in the polishing liquid composition A of the present disclosure can be, for example, the balance with components a1, a2, a3, and optional components described later.

[0064] <Nonionic water-soluble polymer a4 (component a4)> In one or more embodiments, the polishing liquid composition A of the present disclosure preferably further contains a nonionic water-soluble polymer a4 (hereinafter also referred to as "component a4") from the viewpoint of reducing residues on the substrate surface. From the same viewpoint, as component a4, a nonionic water-soluble polymer having an alkylene oxide group, a hydroxyl group, or an amide group in the molecule is preferable. Examples of the alkylene oxide group include an ethylene oxide group and a propylene oxide group. Component a4 may be of one type or a combination of two or more types.

[0065] Examples of component a4 include at least one selected from polyglycerin, polyglycerin alkyl ether, polyglycerin alkyl ester, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyhydroxyethyl acrylamide, and polyethylene glycol from the viewpoint of reducing residues on the substrate surface. From the viewpoints of reducing residues on the substrate surface and suppressing foaming of the polishing liquid, the alkyl group of the polyglycerin alkyl ether preferably has 3 to 22 carbon atoms, more preferably 5 to 16 carbon atoms, and still more preferably 7 to 12 carbon atoms. The alkyl group may be a linear alkyl group or a branched alkyl group. From the viewpoint of improving wettability, the average degree of polymerization of glycerin units in the polyglycerin alkyl ether is 5 or more, preferably 10 or more, more preferably 15 or more, and still more preferably 18 or more. From the viewpoints of improving the polishing rate and reducing residues on the substrate surface, it is 100 or less, preferably 60 or less, more preferably 45 or less, and still more preferably 25 or less. Examples of the polyglycerin alkyl ether include polyglycerin lauryl ether, polyglycerin decyl ether, polyglycerin myristyl ether, and the like. From the viewpoints of reducing residues on the substrate surface and suppressing foaming of the polishing liquid, the alkyl group of the polyglycerin alkyl ester preferably has 3 to 22 carbon atoms, more preferably 5 to 16 carbon atoms, and still more preferably 7 to 12 carbon atoms. The alkyl group may be a linear alkyl group or a branched alkyl group. From the viewpoint of improving wettability, the average degree of polymerization of glycerin units in the polyglycerin alkyl ester is 5 or more, preferably 10 or more, more preferably 15 or more, and still more preferably 18 or more. From the viewpoints of improving the polishing rate and reducing residues on the substrate surface, it is 100 or less, preferably 60 or less, more preferably 45 or less, and still more preferably 25 or less. Examples of the polyglycerin alkyl ester include polyglycerin lauryl ester, polyglycerin decyl ester, polyglycerin myristyl ester, and the like. From the viewpoint of reducing residues on the substrate surface, at least one selected from hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, and hydroxybutyl cellulose is preferable as the hydroxyalkyl cellulose, and hydroxyethyl cellulose (HEC) is more preferable. Among these, from the viewpoints of improving the polishing rate and reducing residues on the substrate surface, polyglycerin is preferable as Component A4.

[0066] From the viewpoint of reducing residues on the substrate surface, the weight-average molecular weight of Component A4 is preferably 300 or more, more preferably 500 or more, still more preferably 1,000 or more, yet more preferably 1,500 or more, and even more preferably 2,000 or more. From the same viewpoint and the viewpoint of the filterability of the polishing liquid, it is preferably less than 500,000, more preferably 400,000 or less, and still more preferably 300,000 or less. When Component A4 is polyglycerin, from the same viewpoint, the weight-average molecular weight of Component A4 is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, and preferably 10,000 or less, more preferably 8,000 or less, and still more preferably 6,000 or less. The weight-average molecular weight of Component A4 can be measured by the method described in the examples below.

[0067] When the polishing liquid composition A of the present disclosure contains Component A4, from the viewpoint of reducing residues on the substrate surface, the content of Component A4 in the polishing liquid composition A of the present disclosure is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.02% by mass or more, and from the same viewpoint, preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and still more preferably 0.03% by mass or less. More specifically, the content of Component A4 in the polishing liquid composition A of the present disclosure is preferably 0.005% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05% by mass or less, and still more preferably 0.02% by mass or more and 0.03% by mass or less. When Component A4 is a combination of two or more, the content of Component A4 refers to their total content.

[0068] <Other Components> The polishing liquid composition A of the present disclosure may further contain other components as long as the effects of the present disclosure are not hindered. Examples of other components include, in one or more embodiments, water-soluble polymers other than Component A2 and Component A4, pH adjusters other than Component A3, preservatives, alcohols, chelating agents, and oxidizing agents.

[0069] <pH of Polishing Liquid Composition A> From the perspective of improving the polishing rate and reducing residues on the substrate surface, the pH of the polishing liquid composition A of the present disclosure is 8 or more, preferably 8.5 or more, more preferably 9 or more, still more preferably 9.5 or more. And from the perspective of the storage stability of the polishing liquid and reducing residues on the substrate surface, it is 12 or less, preferably 11.5 or less, more preferably 11 or less, and still more preferably 10.5. More specifically, the pH of the polishing liquid composition A of the present disclosure is 8 or more and 12 or less, preferably 9 or more and 11.5 or less, more preferably 9.5 or more and 11 or less, and still more preferably 9.5 or more and 10.5 or less. The pH of the polishing liquid composition of the present disclosure can be adjusted using Component C or a known pH adjuster. In the present disclosure, the above pH is the value measured by the method described in the examples.

[0070] The polishing liquid composition A of the present disclosure can be produced, for example, by blending Component a1, Component a2, Component a3, and an aqueous medium, and further, if desired, Component a4 and other components by a known method. That is, the polishing liquid composition A of the present disclosure can be produced, for example, by blending at least Component a1, Component a2, Component a3, and an aqueous medium. Therefore, in one aspect, the present disclosure relates to a method for producing a polishing liquid composition, including a step of blending at least Component a1, Component a2, Component a3, and an aqueous medium. In the present disclosure, "blending" includes mixing Component a1, Component a2, Component a3, the aqueous medium, and, if necessary, Component a4 and other components simultaneously or in any order. The blending can be carried out, for example, using a stirrer such as a homomixer, homogenizer, ultrasonic disperser, wet ball mill, or bead mill. The preferred blending amounts of the respective components in the method for producing the polishing liquid composition A of the present disclosure described above can be the same as the preferred contents of the respective components in the polishing liquid composition A of the present disclosure described above.

[0071] In the present disclosure, the "content of each component in the polishing liquid composition" refers to the content of each component at the time of use, that is, at the time when the use of the polishing liquid composition for polishing is started.

[0072] The polishing liquid composition A of the present disclosure is manufactured as a concentrate from the viewpoints of storage and transportation, and may be diluted during use. From the viewpoints of manufacturing and transportation costs, the dilution ratio is preferably 2 times or more, more preferably 10 times or more, still more preferably 30 times or more, and still more preferably 50 times or more. From the viewpoint of storage stability, it is preferably 180 times or less, more preferably 140 times or less, still more preferably 100 times or less, and still more preferably 70 times or less. The concentrate of the polishing liquid composition A of the present disclosure can be diluted with water so that the content of each component becomes the above-described content (i.e., the content during use) during use. In the present disclosure, "during use" of the concentrate of the polishing liquid composition refers to a state in which the concentrate of the polishing liquid composition is diluted.

[0073] [Rinse agent composition B] The rinse agent composition B used in step (2) contains an anionic polymer b1, a hydrophilic agent b2, and an aqueous medium.

[0074] <Anionic polymer b1 (component b1)> The anionic polymer b1 (hereinafter also referred to as "component b1") contained in the rinse agent composition B of the present disclosure is an anionic polymer having at least one anionic group selected from a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and salts thereof. Examples of the counter ion when the anionic group takes the form of a salt include metal ions, ammonium ions, alkylammonium ions, etc. From the viewpoints of the wettability of the silicon wafer and particle removability, ammonium ions are preferred. Component b1 may be one kind or a combination of two or more kinds.

[0075] As component b1, in one or more embodiments, at least one selected from polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinylphosphonic acid, polyvinylsulfonic acid, polystyrenesulfonic acid, polymers of (meth)2-acrylamido-2-methylpropanesulfonic acid (AMPS), copolymers of (meth)acrylic acid and monomethoxypolyethylene glycol mono(meth)acrylate, copolymers of (meth)acrylate having an anionic group and monomethoxypolyethylene glycol mono(meth)acrylate, copolymers of alkyl (meth)acrylate, (meth)acrylic acid and monomethoxypolyethylene glycol mono(meth)acrylate, copolymers of (meth)acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS), alkali metal salts thereof, and ammonium salts thereof is included. As component b1, in one or more embodiments, formalin condensates having a sulfonic acid group or a salt thereof are included. For example, at least one selected from formalin condensates of phenolsulfonic acid (PhS), formalin condensates of naphthalenesulfonic acid, formalin condensates of bis(4-hydroxyphenyl)sulfone (BisS) and phenolsulfonic acid (PhS) (BisS / PhS), formalin condensates of p-cresol and phenolsulfonic acid (PhS), formalin condensates of bis(4-hydroxy-3-methylphenyl)sulfone (BSDM) and phenolsulfonic acid (PhS), and formalin condensates of phenol (Ph) and phenolsulfonic acid (PhS) is included. Among these, as component b1, from the viewpoint of reducing residues on the substrate surface, at least one selected from polyacrylic acid, polystyrenesulfonic acid, BisS / PhS, and ammonium salts thereof is preferable. When component b1 is BisS / PhS, the molar ratio of BisS to PhS (BisS / PhS) is preferably 10 / 90 to 30 / 70 from the viewpoint of reducing residues on the substrate surface.

[0076] The weight-average molecular weight of component b1 is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, from the viewpoints of the wettability of the silicon wafer and the particle removability, and, from the same viewpoints, preferably 200,000 or less, more preferably 150,000 or less, still more preferably 100,000 or less. The weight-average molecular weight of component b1 can be measured by the method described in the examples.

[0077] The content of component b1 in the rinse agent composition B of the present disclosure is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, still more preferably 0.005% by mass or more, from the viewpoint of particle removability, and, from the same viewpoint, preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less. More specifically, the content of component b1 in the rinse agent composition B of the present disclosure is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.002% by mass or more and 0.5% by mass or less, still more preferably 0.005% by mass or more and 0.1% by mass or less, from the viewpoint of particle removability. When component b1 is a combination of two or more kinds, the content of component b1 refers to their total content.

[0078] <Hydrophilic agent b2 (component b2)> The hydrophilic agent b2 (hereinafter also referred to as "component b2") contained in the rinse agent composition B of the present disclosure is at least one water-soluble polymer selected from polyglycerin, polyglycerin derivatives, polyglycidol, and polyglycidol derivatives. Component b2 may be one kind or a combination of two or more kinds. Examples of the polyglycerin derivative include polyglycerin alkyl ether, polyglycerin dialkyl ether, polyglycerin fatty acid ester, polyethylene oxide-added polyglycerin, polypropylene oxide-added polyglycerin, aminated polyglycerin, and the like. Examples of polyglycidol derivatives include polyglycidol alkyl ethers, polyglycidol dialkyl ethers, polyglycidol fatty acid esters, polyethylene oxide-added polyglycidol, polypropylene oxide-added polyglycidol, aminated polyglycidol, and the like. Among these, from the viewpoints of the wettability and particle removability of the silicon wafer, polyglycerin and polyglycerin derivatives are preferred as component b2, at least one selected from polyglycerin and polyglycerin alkyl ethers is more preferred, and polyglycerin alkyl ether is even more preferred. From the viewpoints of the wettability and particle removability of the silicon wafer, the alkyl group of the polyglycerin alkyl ether preferably has 3 to 22 carbon atoms, more preferably 5 to 16 carbon atoms, and even more preferably 7 to 12 carbon atoms. The alkyl group may be a linear alkyl group or a branched alkyl group. From the viewpoint of the wettability of the silicon wafer, the average degree of polymerization of the glycerin units of the polyglycerin alkyl ether is 5 or more, preferably 10 or more, more preferably 15 or more, and even more preferably 18 or more. From the viewpoints of the wettability and particle removability of the silicon wafer, it is 100 or less, preferably 60 or less, more preferably 45 or less, and even more preferably 25 or less. Examples of the polyglycerin alkyl ether include polyglycerin lauryl ether, polyglycerin decyl ether, polyglycerin myristyl ether, and the like.

[0079] From the viewpoints of the wettability and particle removability of the silicon wafer, the weight average molecular weight of component b2 is preferably 500 or more, more preferably 700 or more, and even more preferably 900 or more. From the same viewpoints, it is preferably 1,500,000 or less, more preferably 500,000 or less, even more preferably 100,000 or less, even more preferably 25,000 or less, and even more preferably 10,000 or less. The weight average molecular weight of component b2 can be measured by the method described in the examples.

[0080] From the viewpoints of the wettability and particle removability of the silicon wafer, the content of component b2 in the rinse agent composition B of the present disclosure is preferably 0.0005% by mass or more, more preferably 0.002% by mass or more, still more preferably 0.005% by mass or more, and from the same viewpoints, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less. More specifically, the content of component b2 in the rinse agent composition B of the present disclosure is preferably 0.0005% by mass or more and 0.5% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, still more preferably 0.005% by mass or more and 0.05% by mass or less. When component b2 is a combination of two or more types, the content of component b2 refers to their total content.

[0081] <aqueous medium> Examples of the aqueous medium contained in the rinse agent composition B of the present disclosure include the same ones as the aqueous medium contained in the polishing liquid composition A of the present disclosure. From the viewpoint of particle removability, water is preferred, ion-exchanged water and ultrapure water are more preferred, and ultrapure water is still more preferred. The content of the aqueous medium in the rinse agent composition B of the present disclosure can be, for example, the balance with components b1, b2, and optional components described later.

[0082] <water-soluble polymer b3 having a betaine structure (component b3)> In one or more embodiments, the rinse agent composition B of the present disclosure preferably further contains a water-soluble polymer b3 having a betaine structure (hereinafter also simply referred to as "component b3") from the viewpoints of the wettability and particle removability of the silicon wafer. In the present disclosure, the betaine structure refers to a structure having a positive charge and a negative charge in the same molecule and the charges being neutralized. The betaine structure preferably has the positive charge and the negative charge at non-adjacent positions, and preferably at positions separated by one or more atoms. Component b3 is a polymer containing a structural unit b3-1 to be described later in one or more embodiments. For example, it includes a homopolymer composed of the structural unit b3-1 to be described later, a copolymer containing the structural unit b3-1 to be described later and the structural unit b3-2 to be described later, a copolymer containing the structural unit b3-1 to be described later and the structural unit b3-3 to be described later, and at least one selected from copolymers containing the structural unit b3-1 to be described later, the structural unit b3-2 to be described later, and the structural unit b3-3 to be described later. Component b3 may be one type or a combination of two or more types.

[0083] (Structural unit b3-1) In one or more embodiments, the structural unit b3-1 is a structural unit derived from a monomer containing a betaine structure from the viewpoints of easy availability of the unsaturated monomer and polymerizability of the monomer. As the betaine structure, a sulfobetaine structure, a carboxybetaine structure, or a phosphobetaine structure is preferable, a carboxybetaine structure or a phosphobetaine structure is more preferable, and a phosphobetaine structure is still more preferable. In the present disclosure, the phosphobetaine structure is due to a phosphate group in which the negative charge of the betaine structure is dissociated, the sulfobetaine structure is due to a sulfonic acid group in which the negative charge of the betaine structure is dissociated, and the carboxybetaine structure is due to a carboxy group in which the negative charge of the betaine structure is dissociated. In one or more embodiments, examples of the structural unit b3-1 derived from a monomer containing a betaine structure include a structural unit represented by the following formula (V). The structural unit b3-1 may be one type or a combination of two or more types.

[0084] [Chemical formula]

[0085] In formula (V), R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group, X 1 represents O or NH, Y1 and Y 2 are the same or different and each represents an alkylene group having 1 to 4 carbon atoms. In formula (I), R 4 and R 5 are each preferably a hydrogen atom from the viewpoints of availability of the unsaturated monomer and polymerizability of the monomer. R 6 is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the same viewpoints. R 7 , R 8 and R 9 are preferably a methyl group from the same viewpoints. X 1 is preferably O (oxygen atom) from the same viewpoints. Y 1 and Y 2 are each preferably an alkylene group having 2 or 3 carbon atoms, more preferably an alkylene group having 2 carbon atoms, from the same viewpoints.

[0086] As the structural unit b3-1, from the viewpoints of availability of the unsaturated monomer and polymerizability of the monomer, there can be mentioned structural units derived from monomers containing a methacryloyloxyethylphosphobetaine structure, for example, structural units derived from monomers such as 2-methacryloyloxyethyl phosphorylcholine (MPC).

[0087] (Structural unit b3-2) The structural unit b3-2 is at least one structural unit selected from the structural unit represented by the following formula (VI), the structural unit represented by the following formula (VII), and the structural unit represented by the following formula (VIII). The structural unit b3-2 may be one kind or a combination of two or more kinds.

[0088] [Chemical formula]

[0089] In formula (VI), R 10 , R 11 and R 12 are the same or different and each represents a hydrogen atom, a methyl group or an ethyl group, X 2 represents O or NH, and R 13represents a hydrocarbon group. In formula (VI), R 10 and R 11 are preferably hydrogen atoms from the viewpoints of availability of the unsaturated monomer and polymerizability of the monomer. R 12 is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the same viewpoints. X 2 is preferably O (oxygen atom) from the same viewpoints. The hydrocarbon group of R 13 may be in any form of linear, branched or cyclic. The hydrocarbon group of R 13 is preferably an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, or an aralkyl group having 7 to 22 carbon atoms, more preferably an alkyl group having 1 to 22 carbon atoms or an aralkyl group having 7 to 22 carbon atoms, from the same viewpoints. Specific examples of R 13 include alkyl groups such as butyl group and aralkyl groups such as benzyl group.

[0090] In formula (VII), R 14 , R 15 and R 16 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and R 17 represents a hydrogen atom, a hydroxyl group, a hydrocarbon group or an alkoxy group. In formula (VII), R 14 and R 15 are preferably hydrogen atoms from the viewpoints of availability of the unsaturated monomer and polymerizability of the monomer. R 16 is preferably a hydrogen atom or a methyl group from the same viewpoints. The hydrocarbon group of R 17 may be in either linear or branched form. Examples of the hydrocarbon group of R 17 include an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms from the same viewpoints. Examples of the alkoxy group of R 17 include, for example, an alkoxy group having 1 to 4 carbon atoms. R 17 is preferably a hydrogen atom from the same viewpoints.

[0091] In formula (VIII), R 18 , R 19 and R 20are the same or different and represent a hydrogen atom, a methyl group, or an ethyl group, and n represents an integer of 2 to 12. In formula (VIII), R 18 , R 19 , and R 20 are preferably hydrogen atoms from the viewpoint of reducing residues on the substrate surface. From the same viewpoint, n is preferably an integer of 2 to 12, more preferably an integer of 3 to 10, and even more preferably 4 to 6.

[0092] As the structural unit represented by formula (VI), in one or more embodiments, there may be mentioned structural units derived from at least one monomer selected from butyl methacrylate (BMA), 2-ethylhexyl methacrylate (EHMA), lauryl methacrylate (LMA), stearyl methacrylate (SMA), and benzyl methacrylate (BzMA). As the structural unit represented by formula (VII), in one or more embodiments, there may be mentioned structural units derived from styrene (St) or α-methylstyrene (αMSt). As the structural unit represented by formula (VIII), in one or more embodiments, there may be mentioned structural units derived from vinylpyrrolidone (VP).

[0093] When component b3 is a copolymer containing structural unit b3-1 and structural unit b3-2, examples of component b3 include at least one selected from 2-methacryloyloxyethyl phosphorylcholine / butyl methacrylate copolymer (MPC / BMA), 2-methacryloyloxyethyl phosphorylcholine / stearyl methacrylate copolymer (MPC / SMA), 2-methacryloyloxyethyl phosphorylcholine / benzyl methacrylate copolymer (MPC / BzMA), 2-methacryloyloxyethyl phosphorylcholine / α-methylstyrene copolymer (MPC / αMSt), and 2-methacryloyloxyethyl phosphorylcholine / vinylpyrrolidone copolymer (MPC / VP).

[0094] When component b3 is a copolymer containing constitutional unit b3-1 and constitutional unit b3-2, the total content (mol%) of constitutional unit b3-1 and constitutional unit b3-2 in all the constitutional units of component b3 is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 99 to 100 mol% from the viewpoint of reducing residues on the substrate surface.

[0095] When component b3 is a copolymer containing constitutional unit b3-1 and constitutional unit b3-2, the molar ratio (b3-1 / b3-2) of constitutional unit b3-1 to constitutional unit b3-2 in all the constitutional units of component b3 is preferably 10 / 90 or more, more preferably 20 / 80 or more, still more preferably 30 / 70 or more, even more preferably 40 / 60 or more, even more preferably 50 / 50 or more, even more preferably 60 / 40 or more, even more preferably 70 / 30 or more from the viewpoint of reducing residues on the substrate surface. From the same viewpoint, it is preferably 98 / 2 or less, more preferably 95 / 5 or less.

[0096] (Constitutional unit b3-3) Constitutional unit b3-3 is a constitutional unit having at least one group selected from a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group, and salts thereof. Examples of the salt include chloride (Cl - ) salt, bromide (Br - ) salt, sulfate (SO4 2- ) salt, etc. Constitutional unit b3-3 may be one kind or a combination of two or more kinds.

[0097] As the monomer forming constitutional unit b3-3, at least one selected from methacryloyloxyethyldimethylethylammonium (MOEDES), 2-hydroxy-3-(trimethylammonio)propyl methacrylate (THMPA), methacryloylethyltrimethylammonium (MOETMA), 2-aminoethyl methacrylate (MOEA), and 2-(diethylamino)ethyl methacrylate (MOEDEA) is preferable from the viewpoint of reducing residues on the substrate surface.

[0098] When component b3 is a copolymer containing structural unit b3-1 and structural unit b3-3, in one or more embodiments, from the perspective of reducing residues on the substrate surface, examples of component b3 include 2-methacryloyloxyethyl phosphorylcholine / methacrylic acid 2-hydroxy-3-(trimethylammonio)propyl copolymer (MPC / THMPA).

[0099] When component b3 is a copolymer containing structural unit b3-1 and structural unit b3-3, the total content (mol%) of structural unit b3-1 and structural unit b3-3 in all the structural units of component b3 is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and still more preferably 99 to 100 mol%.

[0100] When component b3 is a copolymer containing structural unit b3-1 and structural unit b3-3, the molar ratio (b3-1 / b3-3) of structural unit b3-1 to structural unit b3-3 in all the structural units of component b3 is preferably 10 / 90 or more, more preferably 20 / 80 or more, still more preferably 30 / 70 or more, still more preferably 40 / 60 or more, still more preferably 50 / 50 or more, still more preferably 60 / 40 or more, still more preferably 70 / 30 or more from the perspective of reducing residues on the substrate surface. From the same perspective, it is preferably 98 / 2 or less, more preferably 95 / 5 or less.

[0101] Component b3 may further have other structural units other than the above-described structural units b3-1, b3-2, and b3-3. Examples of other structural units include hydroxyethyl methacrylate, acrylonitrile, and the like.

[0102] From the perspective of reducing residues on the substrate surface, the weight average molecular weight of Component B3 is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more. From the same perspective, it is preferably 3,000,000 or less, more preferably 2,000,000 or less, still more preferably 1,000,000 or less. More specifically, the weight average molecular weight of Component B is preferably 1,000 or more and 3,000,000 or less, more preferably 5,000 or more and 2,000,000 or less, still more preferably 10,000 or more and 1,000,000 or less. The weight average molecular weight of Component B can be measured using, for example, gel permeation chromatography (GPC).

[0103] From the perspective of reducing residues on the substrate surface, the content of Component B3 in the rinse agent composition B of the present disclosure is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, still more preferably 0.005% by mass or more. From the same perspective, it is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, still more preferably 0.02% by mass or less. More specifically, the content of Component B3 in the rinse agent composition B of the present disclosure is more preferably 0.001% by mass or more and 0.1% by mass or less, still more preferably 0.002% by mass or more and 0.05% by mass or less, still more preferably 0.005% by mass or more and 0.02% by mass or less. When Component B3 is a combination of two or more types, the content of Component B3 refers to the total content thereof.

[0104] <Other Components> The rinse agent composition B of the present disclosure may further contain other components as long as the effects of the present disclosure are not impaired. As other components, in one or more embodiments, it can further contain at least one optional component selected from water-soluble polymers other than Components B1 to B3, pH adjusters, preservatives, alcohols, chelating agents, defoaming agents, and oxidizing agents.

[0105] <pH of the Rinse Agent Composition B> From the perspective of solution stability, the pH of the rinsing agent composition B of the present disclosure at 25°C is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and from the perspective of the substrate surface quality, it is preferably 11 or less, and more preferably 10 or less. The pH can be adjusted by appropriately adding a pH adjuster as necessary. Here, the pH at 25°C can be measured using a pH meter, specifically, it can be measured by the method described in the examples.

[0106] <Method for manufacturing a rinsing agent composition> The rinsing agent composition of the present disclosure can be produced, for example, by a production method including a step of mixing component b1, component b2, an aqueous medium, and optional components (component b3, other components) as necessary by a known method. In the present disclosure, "mixing" includes mixing component b1, component b2, the aqueous medium, and optional components (component b3, other components) as necessary simultaneously or in any order. The mixing can be performed, for example, using a mixer such as a homomixer, homogenizer, ultrasonic disperser, and wet ball mill. The preferable mixing amounts of the respective components in the production method of the rinsing agent composition of the present disclosure can be the same as the preferable contents of the respective components in the rinsing agent composition of the present disclosure described above.

[0107] In the present disclosure, "the content of each component in the rinsing agent composition" refers to the content of each component at the time of use of the rinsing agent composition, that is, at the time when the rinsing agent composition is used for rinsing treatment.

[0108] <Concentrate of rinsing agent composition> The rinsing agent composition B of the present disclosure may be stored and supplied in a concentrated state as long as its storage stability is not impaired. In this case, it is preferable in terms of further reducing the production and transportation costs. The concentrate of the rinsing agent composition of the present disclosure may be appropriately diluted with water so that the content of each component becomes the content of each component described above at the time of use. From the perspective of further reducing the production and transportation costs, the concentration ratio is preferably 2 times or more, more preferably 10 times or more, and still more preferably 20 times or more.

Examples

[0109] Hereinafter, the present disclosure will be described in more detail by way of examples. However, these are illustrative and the present disclosure is not limited to these examples.

[0110] 1. Preparation of polishing liquid composition A The silica particles shown in Table 1 (component a1), the water-soluble polymer shown in Table 1 (component a2 or non-component a2), ammonia (component a3), the nonionic water-soluble polymer shown in Table 1 (component a4), and ultrapure water were stirred and mixed to obtain the polishing liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 3. In Table 1, the content of each component in the polishing liquid composition A is the content (mass%, active ingredient) of each component at the time of use of the polishing liquid composition. The content of ultrapure water is the remainder excluding component a1, component a2 or non-component a2, component a3, and component a4. The pH of each polishing liquid composition (at the time of use) at 25°C was 10.3.

[0111] The following were used for component a1, component a2, non-component a2, component a3, and component a4 used in the preparation of each polishing liquid composition A. (Component a1) Colloidal silica [average primary particle size 25 nm, average secondary particle size 49 nm, degree of aggregation 2.0] (Component a2) Cation-modified PVA (cation modification rate: 0.22 mol%) [manufactured by Mitsubishi Chemical Corporation, OKS-6223, weight average molecular weight 85,000] Glycidol-modified polyallylamine (modification rate 1.5) [manufactured by Nitto Boehringer Medical Co., Ltd., weight average molecular weight 26,000] Glycidol-modified polyallylamine (modification rate 2.0) [manufactured by Nitto Boehringer Medical Co., Ltd., weight average molecular weight 55,000] Methyldiallylamine·sulfur dioxide copolymer [manufactured by Nitto Boehringer Medical Co., Ltd., weight average molecular weight 3,000] (Non-component a2) HEC (hydroxyethyl cellulose) [manufactured by Daicel Corporation, SE400, weight average molecular weight 250,000] (Component a3) Ammonia [28 mass% aqueous ammonia, manufactured by Kishida Chemical Co., Ltd., reagent special grade] (Component a4) Polyglycerin ["XPW" manufactured by Daicel Corporation, degree of polymerization 40, weight average molecular weight 2,980] PEG (polyethylene glycol) [manufactured by NOF Corporation, weight average molecular weight 6,000]

[0112] 2. Preparation of Rinsing Agent Composition B (Examples 1 to 9 and Comparative Examples 1 to 3) The anionic polymer (Component b1) shown in Table 1, the hydrophilizing agent b2 (Component b2) shown in Table 1, the water-soluble polymer b3 (Component b3) containing a betaine structure shown in Table 1, and ultrapure water were stirred and mixed, and the pH at 25°C was adjusted to 5.0 using a pH adjuster (ammonia) as necessary to obtain the rinsing agent compositions of Examples 1 to 9 and Comparative Examples 1 to 3. In Table 1, the content of each component in the rinsing agent composition B is the content (mass%, active ingredient) of each component at the time of use of the rinsing agent composition. The content of ultrapure water is the remainder excluding Component b1, Component b2, Component b3, and the pH adjuster.

[0113] The following were used for Component b1, Component b2, and Component b3 used in the preparation of each rinsing agent composition B. (Component b1) Ammonium polyacrylate [manufactured by Kao Corporation, weight average molecular weight 37,000] Polystyrene sulfonic acid [manufactured by Tosoh Corporation, weight average molecular weight 70,000] BisS / PhS [condensate of bis(4-hydroxyphenyl) sulfone and phenol sulfonic acid, molar ratio (BisS / PhS): 20 / 80, manufactured by Konishi Chemical Industry Co., Ltd., weight average molecular weight 5,000] (Component b2) Polyglycerin (20) lauryl ether [manufactured by Daicel Corporation, weight average molecular weight 2,000] (Component b3) MPC / BMA copolymer [trade name Lipidure-PMB, manufactured by NOF Corporation, molar ratio (MPC / BMA): 80 / 20, weight average molecular weight 400,000]

[0114] 3. Measurement Methods for Various Parameters [pH of Polishing Liquid Composition and Rinsing Agent Composition] The pH value at 25°C of the abrasive liquid composition or the rinse agent composition is the value measured using a pH meter (manufactured by Toa Denpa Kogyo Co., Ltd., "HM-30G"), and is the numerical value after 1 minute of immersing the electrode of the pH meter in the abrasive liquid composition or the rinse agent composition.

[0115] [Average primary particle diameter of silica particles (component a1)] The average primary particle diameter (nm) of component a1 is calculated by the following formula using the specific surface area S (m 2 / g) obtained by the BET (nitrogen adsorption) method. Average primary particle diameter (nm) = 2727 / S

[0116] The specific surface area S of component a1 is measured by the nitrogen adsorption method (BET method) using a specific surface area measuring device (Micromeritics automatic specific surface area measuring device "FlowSorb III 2305", manufactured by Shimadzu Corporation) after performing the following [Pretreatment], accurately weighing approximately 0.1 g of the measurement sample to four decimal places in the measurement cell, and drying it in an atmosphere of 110°C for 30 minutes immediately before measuring the specific surface area. [Pretreatment] (a) Adjust the slurry-like component a1 to pH 2.5 ± 0.1 with an aqueous nitric acid solution. (b) Take the slurry-like component a1 adjusted to pH 2.5 ± 0.1 in a petri dish and dry it in a hot air dryer at 150°C for 1 hour. (c) After drying, finely pulverize the obtained sample with an agate mortar. (d) Suspend the pulverized sample in ion-exchanged water at 40°C and filter it through a membrane filter with a pore size of 1 μm. (e) Wash the filtrate on the filter 5 times with 20 g of ion-exchanged water (40°C). (f) Take the filter with the filtrate attached in a petri dish and dry it in an atmosphere of 110°C for 4 hours. (g) Take the dried filtrate (component a1) so that no filter debris is mixed in, and finely pulverize it with a mortar to obtain a measurement sample.

[0117] [Average secondary particle diameter of silica particles (component a1)] The average secondary particle diameter (nm) of Component A1 was measured using the dynamic light scattering method (apparatus name: "Zetasizer Nano ZS", manufactured by Sysmex Corporation) after adding the abrasive to ion-exchanged water so that the concentration of Component A1 became 0.25% by mass, and then filling the obtained aqueous dispersion into a Disposable Sizing Cuvette (10 mm cell made of polystyrene) up to a height of 10 mm from the bottom.

[0118] [Measurement of the weight-average molecular weight of the water-soluble polymer] The weight-average molecular weight of the water-soluble polymer (Component A2, non-Component A2, Component A4, Component B1, Component B2, Component B3) was calculated based on the peak in the chromatogram obtained by applying the gel permeation chromatography (GPC) method under the following conditions. <Measurement conditions for Component A2> Apparatus: HLC-8320 GPC (manufactured by Tosoh Corporation, detector-integrated type) Column: α-M + α-M Eluent: 0.15 mol / L Na2SO4, 1% CH3COOH / water Flow rate: 1.0 mL / min Column temperature: 40 °C Detector: Shodex RI SE-61 differential refractive index detector Standard substance: Monodisperse polyethylene glycol with a known molecular weight <Measurement conditions for non-Component A2, Component A4, Component B1, Component B2> Apparatus: HLC-8320 GPC (manufactured by Tosoh Corporation, detector-integrated type) Column: GMPWXL + GMPWXL (anion) Eluent: 0.2 M phosphate buffer / CH3CN = 9 / 1 Flow rate: 0.5 mL / min Column temperature: 40 °C Detector: Shodex RI SE-61 differential refractive index detector Standard substance: Monodisperse polyethylene glycol with a known molecular weight <Measurement conditions for Component B3> Apparatus: HLC-8320 GPC (manufactured by Tosoh Corporation, detector-integrated type) Column: Two TSKgel α-M (manufactured by Tosoh Corporation) connected in series Eluent: 0.15 mol / L Na2SO4, 1% CH3COOH / water Flow rate: 1.0 mL / min Column temperature: 40 °C Detector: Shodex RI SE-61 differential refractive index detector Standard substance: Monodisperse pullulan with known molecular weight

[0119] [Cation modification rate of cationized PVA] (i) Weigh accurately 1 - 5 mg of the sample using an ultra-microbalance. Decompose the sample in an argon-oxygen stream in the presence of a catalyst to convert it to NO. Measure the chemiluminescence intensity generated when this NO reacts with ozone to determine the nitrogen content. The combustion and decomposition of the sample were carried out manually while checking the sample status. At this time, it was confirmed visually and by detection intensity that no incomplete combustion occurred. Measuring device: TN-10 manufactured by Mitsubishi Chemical Analytech Co., Ltd. Electric furnace setting conditions: INLET 800 °C : OUTLET 900 °C Gas flow rate: O2 MAIN 300 ml / min : Ar 1 L / min : O2 0.5 L / min Calibration curve adjustment method: A solution of aniline dissolved in toluene was used as the calibration curve sample. (ii) On the other hand, burn 100 mg of the sample in an oxygen stream and absorb the generated gas with 3% hydrogen peroxide solution. Measure the chloride ions in the absorption solution by ion chromatography to determine the chlorine concentration. Combustion device: QS-AB2 manufactured by Yoshida Scientific Instruments Co., Ltd. Combustion temperature: PREH 400 °C : HIH 1000 °C Combustion gas flow rate: 2.5 L / min (Ar) Measuring device: ICS-2000 manufactured by Dionex Separation column: IonPack AS418 Guard column: IonPack AG18 Eluent: 30 mM KOH Detector: Conductivity detector (C) The cationized PVA contains N and Cl in a molar ratio of 1:1, and each of the supply sources of the structural units containing cationic groups contains one N atom and one Cl atom. Therefore, the content (mol%) of the cationic groups was calculated from each of the nitrogen amount and the chlorine concentration, and the average value was taken as the amount (mol%) of the structural units containing cationic groups (cationic modification rate).

[0120] [Glycidol modification rate] The glycidol modification rate was 13 determined using 13C-NMR. [Measurement conditions] Sample: 200 mg of glycidol-modified polyallylamine was dissolved in 0.6 mL of heavy water Apparatus used: 400 MHz 13 13C-NMR (Agilent 400-MR DD2 manufactured by Agilent Technologies, Inc.) Measurement conditions: 13 13C-NMR measurement, pulse interval time 5 seconds, tetramethylsilane as the standard peak (σ: 0.0 ppm) was measured Number of integration times: 5000 times Each peak range used for integration: A: 71.0 to 72.3 ppm (integrated value of the peak of the C to which the secondary hydroxyl group of glycidol reacted with the amino group is bonded) B: 32.0 to 41.0 ppm (integrated value of the peak of the main chain C of allylamine) [Glycidol modification rate] The glycidol modification rate (equivalent ratio of glycidol to the equivalent of amino groups) is determined by the following formula. Glycidol modification rate (equivalent ratio) = 2A / B

[0121] [Measurement of zeta potential of silica particles and polished silicon substrate] Each of the aqueous dispersions shown below was placed in a capillary cell DTS1070, and the zeta potential was measured under the following conditions using a zeta sizer Nano ZS [manufactured by Malvern]. Sample: Refractive index: 1.450 Absorbance: 0.010 Dispersion medium: Viscosity: 0.8872 cP, Refractive index: 1.330, Dielectric constant: 78.5 Temperature: 25°C (1) Surface zeta potential in the polishing process (Zeta potential ζ of silica particles on the surface) The polishing liquid compositions (in use) of Examples 1 to 9 and Comparative Examples 1 to 3 were used as they were as the aqueous dispersion for measuring the zeta potential of silica particles, and the zeta potential ζ of silica particles on the surface was measured. (Zeta potential ζ of Si powder surface Si powder) In ion-exchanged water, water-soluble polymers (component a2, non-component a2, component a4) and ammonia (component a3) formulated in the polishing liquid composition A described in Examples 1 to 9 and Comparative Examples 1 to 3 were added so as to have the contents shown in Table 1, and then 0.1% by mass of fine particles of a single-crystalline silicon substrate pulverized by a bead mill was added. By filtering with a syringe filter (manufactured by Sartorius, pore size 1.2 μm), an aqueous dispersion for measuring the zeta potential of the single-crystalline silicon substrate was prepared, and the zeta potential ζ of Si powder surface Si powder was measured. (2) Surface zeta potential in the rinsing process (Zeta potential ζ of silica particles on the surface) To the polishing liquid compositions (in use) of Examples 1 to 9 and Comparative Examples 1 to 3, components b1, b2, and b3 formulated in the corresponding rinsing agent composition B were added so as to have the contents shown in Table 1, and an aqueous dispersion for measuring the zeta potential of silica particles was prepared. Using this, the zeta potential ζ of silica particles on the surface was measured. (Zeta potential ζ of Si powder surface Si powder) To ion-exchanged water, water-soluble polymers (component a2, non-component a2, component a4) and ammonia (component a3) formulated in the polishing liquid compositions A described in Examples 1 to 9 and Comparative Examples 1 to 3 were added so as to have the contents shown in Table 1, and then 0.1% by mass of fine particles of a single-crystal silicon substrate pulverized with a bead mill was added to prepare an aqueous dispersion of the single-crystal silicon substrate. Further, components b1, b2, and b3 formulated in the corresponding rinse agent compositions B were added so as to have the contents shown in Table 1, and the mixture was filtered through a syringe filter (pore size 1.2 μm, manufactured by Sartorius) to prepare an aqueous dispersion for measuring the zeta potential of the single-crystal silicon substrate, and the zeta potential ζ of the Si powder surface was measured. Si The powder was measured.

[0122] 4. Evaluation of the polishing liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 3 (1) Polishing method For each polishing liquid composition, filtration was performed with a filter (compact cartridge filter "MCP-LX-C10S", manufactured by Advantec) immediately before polishing, and finish polishing was performed on the following silicon substrate to be polished under the following polishing conditions. <Silicon substrate to be polished> Single-crystal silicon substrate [silicon single-sided mirror substrate 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] The above single-crystal silicon substrate was pre-polished using a commercially available polishing liquid composition (manufactured by Fujimi Incorporated, GLANZOX 1302). The haze of the single-crystal silicon substrate after the rough polishing was completed and before the finish polishing was 2 to 3 ppm. <Finish polishing conditions> Polishing machine: Single-sided 8-inch polishing machine "GRIND-X SPP600s" (manufactured by Okamoto Works) Polishing pad: Suede pad (manufactured by Fujibo Ehime Co., Ltd., hardness: 44, thickness: 1.5 mm, compression ratio: 12%, compression elastic modulus: 86%, aperture diameter: 45 μm) Load: 100 g / cm 2 Platen rotation speed: 60 rpm Polishing time: 5 minutes Supply rate of the polishing liquid composition: 100 mL / min (0.32 mL / min per 1 cm of the substrate to be polished) 2 Temperature of the polishing liquid composition: 23 °C Carrier rotation speed: 62 rpm <Measurement of the surface roughness (haze) of the silicon substrate> 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.

[0123] (2) Rinsing method The silicon wafer after the above-mentioned finish polishing (a single-sided mirror-polished silicon wafer with a diameter of 200 mm, conductivity type: P, crystal orientation: 100, resistivity of 0.1 Ω·cm or more and less than 100 Ω·cm) was rinsed under the following conditions using each rinsing agent composition (pH 3.3). <Rinsing conditions> Polishing machine: The same polishing machine as the one used for finish polishing Polishing pad: The same polishing pad as the one used for finish polishing Load: 40 g / cm 2 Platen rotation speed 40 rpm Rinsing time 20 seconds Supply rate of the rinsing agent composition: 1000 mL / min Temperature of the rinsing agent composition: 23 °C Carrier rotation speed: 42 rpm

[0124] (3) Cleaning method ​After the rinsing process, the silicon substrate was subjected to ozone cleaning and diluted hydrofluoric acid cleaning as follows. In the ozone cleaning, an aqueous solution containing 20 ppm of ozone was sprayed from a nozzle toward the center of the silicon substrate rotating at 600 rpm with a flow rate of 1 L / min for 3 minutes. At this time, the temperature of the ozone water was normal temperature. Next, diluted hydrofluoric acid cleaning was performed. In the diluted hydrofluoric acid cleaning, an aqueous solution containing 0.5 mass% of ammonium hydrogen fluoride (special grade, Nacalai Tesque, Inc.) was sprayed from a nozzle toward the center of the silicon substrate rotating at 600 rpm with a flow rate of 1 L / min for 6 seconds. The above ozone cleaning and diluted hydrofluoric acid cleaning were performed as one set, and a total of 2 sets were performed, and finally spin drying was performed. In the spin drying, the silicon substrate was rotated at 1,500 rpm.

[0125] [Evaluation of Wettability] The area of the hydrophilic part (the wetted part) of the mirror surface of the silicon wafer (diameter 200 mm) immediately after finish polishing was visually observed, and the wettability was evaluated according to the following evaluation criteria, and the results are shown in Table 1. [Evaluation Criteria] ◎: The ratio of the wetted area is 90% or more (the water-repellent part is less than 1 cm from the outer circumference of the silicon wafer) ○: The ratio of the wetted area is clearly more than half and less than 90% △: The ratio of the wetted area is approximately half ×: The ratio of the wetted area is clearly less than half

[0126] [Particle Removal Performance] For the particle removal performance of the surface of the silicon wafer after cleaning, the value in the dark field wide oblique incidence channel (DWO) measured using Surfscan SP1-DLS (trade name) manufactured by KLA Tencor was used. The particle removal performance was evaluated by measuring the number of particles with a particle diameter of 45 nm or more on the surface of the silicon wafer. The smaller the LPD value (number of particles), the better the particle removal performance. The measurement was performed on two silicon wafers each, and the average value was calculated, and the particle removal performance was evaluated according to the following evaluation criteria, and the results are shown in Table 1. [Evaluation Criteria] ◎: When the number of particles is less than 200 ○: When the number of particles is 200 or more and less than 500 △: When the number of particles is 500 or more and less than 1000 ×: When the number of particles is 1000 or more

[0127]

Table 1

[0128] As shown in Table 1, it was found that Examples 1 to 9 had better wettability and improved particle removability compared to Comparative Examples 1 to 3.

Industrial Applicability

[0129] By using the method for manufacturing a silicon substrate of the present disclosure, residues on the substrate surface can be reduced. Therefore, in the method for manufacturing a semiconductor substrate such as a silicon wafer, it contributes to improving productivity and reducing costs, and is useful.

Claims

1. Step (1) of polishing a silicon substrate to be polished using a polishing liquid composition A; Step (2) of rinsing the polished silicon substrate using a rinsing agent composition B; Step (3) of cleaning the rinsed silicon substrate, and the method for manufacturing a silicon substrate includes: The polishing liquid composition A in step (1) contains silica particles a1, a water-soluble polymer a2, a nitrogen-containing basic compound a3, and an aqueous medium. The water-soluble polymer a2 is a water-soluble polymer containing an amino group or a quaternary ammonium group. The pH of the polishing liquid composition A is 8 or more and 12 or less. The rinsing agent composition B in step (2) contains an anionic polymer b1, a hydrophilizing agent b2, and an aqueous medium. The anionic polymer b1 is an anionic polymer having at least one anionic group selected from a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, and salts thereof. The hydrophilizing agent b2 is at least one water-soluble polymer selected from polyglycerin, polyglycerin derivatives, polyglycidol, and polyglycidol derivatives. A method for manufacturing a silicon substrate.

2. The method for manufacturing a silicon substrate according to claim 1, wherein the rinsing agent composition B further contains a water-soluble polymer b3 containing a betaine structure.

3. The method for manufacturing a silicon substrate according to claim 1 or 2, wherein the water-soluble polymer a2 contains a structural unit derived from one or more monomers selected from allylamine and diallylamine.

4. The method for manufacturing a silicon substrate according to claim 3, wherein at least a part of the amino groups in the structural unit derived from allylamine has a steric shielding group.

5. The method for manufacturing a silicon substrate according to any one of claims 1 to 4, wherein the content of the water-soluble polymer b1 in the rinsing agent composition B is 0.001% by mass or more and 1% by mass or less.

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