KR20190075897A - Rinse composition for silicon wafers - Google Patents

Abstract

The rinse composition for a silicon wafer of the present invention is a rinse composition for a silicon wafer comprising a water-soluble polymer and water, wherein the water-soluble polymer comprises the water-soluble polymer, silica particles, water and, if necessary, hydrochloric acid or ammonia, The zeta potential Z of the water-soluble polymer-containing silica aqueous dispersion (aqueous dispersion S) having a concentration of the water-soluble polymer of 0.1% by mass, a concentration of the silica particles of 0.1% by mass and a pH at 25 캜 of 7.0, (Z - Z) of the zeta potential Z ₀ of the silica aqueous dispersion (aqueous dispersion S ₀ ) which is composed of hydrochloric acid or ammonia and which has a concentration of the silica particles of 0.1% by mass and a pH of 7.0 at 25 ° C, ₀ ) is 25 ㎷ or less.

Description

Rinse composition for silicon wafers

The present invention relates to a rinse composition for a silicon wafer, a rinsing method of a silicon wafer using the rinse composition, a method of manufacturing a silicon wafer, and a method of manufacturing a semiconductor substrate.

BACKGROUND ART [0002] In recent years, design rules for semiconductor devices have been made finer in response to a demand for higher recording capacity of semiconductor memories. Therefore, the depth of focus becomes shallow in the photolithography performed in the process of manufacturing the semiconductor device, and the demand for reduction of surface defects (LPD: light point defects) and surface roughness (haze) of silicon wafers It is becoming.

For the purpose of improving the quality of a silicon wafer, a polishing step of polishing a silicon wafer includes a lapping (rough polishing) step of planarizing a silicon wafer obtained by slicing a silicon single crystal ingot into a thin disk, And thereafter a finish polishing process for mirror-polishing the surface of the silicon wafer. Particularly, finish polishing performed at the final stage of polishing is carried out for the purpose of suppressing haze and suppressing LPD such as particles, scratches, pits and the like by wettability improvement (hydrophilization) of the surface of a polished silicon wafer.

As a polishing liquid composition used for polishing a silicon wafer, a polishing liquid containing silica particles, hydroxyethyl cellulose (HEC), polyethylene oxide and an alkaline compound has been disclosed for the purpose of improving the haze level (Patent Document 1). The ratio of the number of oxygen atoms derived from a hydroxyl group to the number of oxygen atoms derived from a polyoxyalkylene (the number of oxygen atoms derived from a hydroxyl group / poly (The number of oxygen atoms derived from an oxyalkylene) within a predetermined range is disclosed in Patent Document 2 (Patent Document 2). A polyvinyl alcohol resin having a 1,2-diol structure in a side chain and a zeta potential of a surface in a solution having a pH of 2.0 or more are used for the purpose of reducing contamination on the surface of the polished smear while suppressing aggregation of the abrasive grains. (Abrasive grains) whose surface is chemically modified so as to have a minus value and no isoelectric point (Patent Document 3). There is disclosed a polishing composition for a silicon wafer which contains hydroxypropyl methylcellulose and has abrasive grains having a negative zeta potential in the abrasive liquid composition for the purpose of suppressing the decrease in smoothness and reducing the number of defects (Patent Document 4). It is possible to remove contaminants on the surface of the substrate for a semiconductor device after the CMP process and further to clean the surface of the substrate in a short time, The present invention relates to a process for producing a semiconductor device, which comprises the steps of: preparing a microcapsule containing a polyethylene oxide-polypropylene oxide block copolymer as a polymer flocculant and enlarging the particle size of the microparticles by agglomeration, A substrate cleaning liquid for a device has been disclosed (Patent Document 5).

Japanese Patent Application Laid-Open No. 2004-128089 WO2015 / 060293 WO2014 / 084091 Japanese Patent Application Laid-Open No. 2014-154707 Japanese Laid-Open Patent Publication No. 2012-94852

In the alkaline condition, the surface charges of the silica particles and the silicon wafer are negatively charged together, and due to the charge repulsion, the silica particles can not approach the silicon wafer and the polishing rate can not be sufficiently developed. However, , Adsorbed on both surfaces of the silicon wafer and the silica particles, the charge repulsion of the silicon wafer and the silica particles is suppressed, the binder effect is developed, and the contribution to the improvement of the polishing rate of the silicon wafer is contributed.

However, since the polymer is attached to the surface of the silicon wafer polished in the polishing process (hereinafter also referred to as " polished silicon wafer "), water is supplied between the silicon wafer and the pad after polishing, The silica particles are reattached to the surface of the silicon wafer even when a so-called water rinse is carried out in which the pad is brought into relative motion with respect to the silicon wafer after the polishing in a state in which the rear silicon wafer and the pad are in contact with each other. It takes a considerable amount of time, which has hindered productivity and cost reduction.

Therefore, in the present invention, a rinse composition for a silicon wafer, which makes it possible to shorten the cleaning time of a silicon wafer after polishing and reduce LPD, and a rinsing method of a silicon wafer using the same, a method of manufacturing a silicon wafer, ≪ / RTI >

The rinse composition for a silicon wafer of the present invention is a rinse composition for a silicon wafer comprising a water-soluble polymer and an aqueous medium,

The water-

Wherein the water-soluble polymer is composed of the water-soluble polymer, silica particles, water and, if necessary, hydrochloric acid or ammonia, the concentration of the water-soluble polymer is 0.1 mass%, the concentration of the silica particles is 0.1 mass% Containing zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide and zirconium oxide. Wherein the difference (Z - Z ₀ ) between the zeta potentials Z ₀ of the aqueous dispersion (aqueous dispersion S ₀ ) is not more than 25 수용 is a rinse composition for a silicon wafer.

The rinse composition for a silicon wafer of the present invention is a rinse composition for a silicon wafer comprising a water-soluble polymer and an aqueous medium,

Wherein the water-soluble polymer is at least one selected from the group consisting of polyglycerin, polyglycerin derivatives, polyglycidol, polyglycidol derivatives, polyvinyl alcohol derivatives, and polyacrylamides. .

The rinsing method of a silicon wafer of the present invention includes a step of rinsing a polished silicon wafer using the rinsing composition for a silicon wafer of the present invention.

When the water-soluble polymer contained in the rinse composition for a silicon wafer of the present invention is referred to as a water-soluble polymer A,

A polishing step of polishing a silicon wafer to be polished using a polishing liquid composition comprising silica particles, a water-soluble polymer B and a nitrogen-basic compound and an aqueous medium;

A rinsing step of rinsing the polished silicon wafer with the rinsing composition of the present invention,

And a cleaning step of cleaning the rinsed silicon wafer.

The water-soluble polymer A and the water-soluble polymer B may be the same or different.

The method for manufacturing a semiconductor substrate of the present invention includes a step of rinsing a polished silicon wafer using the rinsing composition for a silicon wafer of the present invention.

A manufacturing method of a semiconductor substrate of the present invention includes a step of manufacturing a silicon wafer by a manufacturing method of the silicon wafer of the present invention.

According to the present invention, it is possible to provide a rinse composition for a silicon wafer, which can shorten the cleaning time of a silicon wafer after polishing and reduce LPD, and a rinsing method of a silicon wafer using the rinse composition for the silicon wafer, And a method of manufacturing a semiconductor substrate.

In the present invention, a rinse composition for a silicon wafer (hereinafter abbreviated as "rinse composition" in some cases) is a specific water-soluble polymer comprising the water-soluble polymer, silica particles, water and, if necessary, hydrochloric acid or ammonia , The zeta potential Z of the water-soluble polymer-containing silica aqueous dispersion (aqueous dispersion S) having a concentration of the water-soluble polymer of 0.1% by mass, a concentration of the silica particles of 0.1% by mass and a pH at 25 ° C of 7.0, (Z - Z) of the zeta potential Z ₀ of the silica aqueous dispersion (aqueous dispersion S ₀ ) composed of water and, if necessary, hydrochloric acid or ammonia and having a silica particle concentration of 0.1% by mass and a pH at 25 ° C of 7.0, Z ₀₎ is, in some cases referred to as the water-soluble polymer (hereinafter referred to as "water-soluble polymer a 'having a property to be not more than 25 ㎷.) after the polishing, by the inclusion of silicon-way Of enabling a reduction in the shortening of the cleaning time and LPD, based on the knowledge that.

The mechanism for expressing the effect of the present invention that can reduce the LPD of the silicon wafer after polishing and shorten the cleaning time when the rinse treatment is performed on the silicon wafer after polishing using the rinse composition of the present invention , It is estimated as follows.

When the rinsing composition of the present invention is supplied and the rinsing treatment using the rinsing composition is started, the surface of the silicon wafer and the silica particles after polishing are polished by the physical force when the pads are moved relative to the silicon wafer after polishing The water-soluble polymer B, which is a component of the polishing liquid composition, is replaced with the water-soluble polymer A. Since the reattachment of the silica particles onto the surface of the silicon wafer is suppressed after the polishing of the silica particles, the residual amount of the silica particles on the silicon wafer after polishing, which is provided in the cleaning step, can be remarkably reduced. Further, The zeta potential of the silica particles can be maintained at a large value without significantly changing the zeta potential of the silica particles, and hence the aggregation of the silica particles is also suppressed. Therefore, it is presumed that the rinse composition of the present invention contains the water-soluble polymer A, thereby realizing the reduction of the LPD of the silicon wafer after polishing and the shortening of the cleaning time.

[Composition for rinse]

The rinse composition of the present invention includes water-soluble polymer A, an aqueous medium, and optional components to the extent that the effect of the present invention is not disturbed. Details of arbitrary components will be described later.

[Water-soluble polymer A]

The water-soluble polymer A is a water-soluble polymer having a property that the difference (Z - Z ₀ ) between the zeta potential Z of the aqueous dispersion S and the zeta potential Z ₀ of the aqueous dispersion S ₀ is 25 ㎷ or less. Here, the aqueous dispersion liquid S is composed of the water-soluble polymer A, silica particles, water and, if necessary, hydrochloric acid or ammonia, and the concentration of the water-soluble polymer A is 0.1 mass%, the concentration of the silica particles is 0.1 mass% containing water-soluble polymer-containing silica aqueous dispersion having a pH of 7.0. The aqueous dispersion S ₀ is a silica aqueous dispersion liquid comprising silica particles, water and, if necessary, hydrochloric acid or ammonia, the concentration of the silica particles being 0.1% by mass and the pH at 25 캜 being 7.0. The zeta potential can be measured by the method described in the examples. When the water-soluble polymer A is composed of two or more water-soluble polymers, the mixture of two or more water-soluble polymers has a property that the difference (Z - Z ₀ ) is 25 ㎷ or less. When the water-soluble polymer A is a mixture of two or more water-soluble polymers, the "concentration of the water-soluble polymer A is 0.1 mass%" means that the concentration of the mixture in the aqueous dispersion S is 0.1 mass% In other words, it means that the total concentration of each of the water-soluble polymers in the aqueous dispersion S is 0.1% by mass.

When the water-soluble polymer A is composed only of the water-soluble polymer a1 described later, the difference (Z - Z ₀ ) is preferably 25 ㎷ or less, preferably 15 ㎷ or less, more preferably 9 ㎷ or less, Or less, more preferably 7 ㎷ or less.

When the water-soluble polymer A is a mixture of the water-soluble polymer a1 and the water-soluble polymer a2 described later, the difference (Z - Z ₀ ) is preferably 25 ㎷ or less, more preferably 15 ㎷ or less Preferably 12 ㎷ or less, more preferably 9 ㎷ or less.

The zeta potential Z ₀ of the aqueous dispersion S ₀ is a predetermined value within a range of, for example, -40 ㎷ to -50 ㎷. As an example thereof, the zeta potential Z ₀ of the aqueous dispersion So is adjusted by using a silica stock solution (PL- (For example, -46 ㎷) of the aqueous dispersion S ₀ .

If the water-soluble polymer A, containing only a water-soluble polymer a1, which will be described later, the water-soluble polymer A is, in terms of aggregation inhibition of silica particles, the secondary particle diameter d and the silica particles in the aqueous dispersion S ₀ of the silica particles in the aqueous dispersion S Is a water-soluble polymer having a ratio (d / d ₀ ) of the secondary particle diameter d ₀ of the water-soluble polymer to the water-soluble polymer of preferably 1.35 or less, more preferably 1.17 or less, further preferably 1.10 or less, further preferably 1.08 or less, From the viewpoint of reducing LPD, it is preferably at least 1.00, more preferably at least 1.02, further preferably at least 1.04, even more preferably at least 1.05.

When the water-soluble polymer A is a mixture of the water-soluble polymer a1 to be described later and the water-soluble polymer a2 described later, the water-soluble polymer A is preferably a water-soluble polymer having a secondary particle diameter d of the silica particles in the aqueous dispersion S, dispersion S 2 ratio (d / d ₀₎ of the primary particle size d ₀ of the silica particles in the _0, preferably 1.35 or less, more preferably 1.34 or less, more preferably 1.33 or less, and more preferably, 1.32 or less Soluble polymer which is a water-soluble polymer which has a viscosity of preferably not less than 1.00, more preferably not less than 1.25, more preferably not less than 1.30, still more preferably not less than 1.31, from the viewpoint of LPD reduction.

Dispersion S ₀ 2 primary particle size d ₀ of the silica particles in, for example, a predetermined value in the range of 64 ~ 73 ㎚, preferably a predetermined value in the range of 66 ~ 69 ㎚, as an example, of silica (For example, 68.4 nm) of the silica particles in the aqueous dispersion S ₀ containing the undiluted solution ("PL-3" manufactured by Fuso Chemical Co., Ltd.) as a source of the silica particles.

The content of the water-soluble polymer A in the rinse composition is preferably 0.001% by mass or more, more preferably 0.015% by mass or more, and still more preferably 0.020% by mass or more, from the viewpoints of shortening the cleaning time and reducing LPD , More preferably not less than 0.025 mass%, even more preferably not less than 0.03 mass%, and from the same viewpoint, preferably not more than 1.0 mass%, more preferably not more than 0.7 mass%, further preferably not more than 0.4 By mass or less, more preferably 0.1% by mass or less, and even more preferably 0.08% by mass or less.

The water-soluble polymer A is preferably selected from the group consisting of polyglycerol, polyglycerin derivatives, polyglycidol, polyglycidol derivatives, polyvinyl alcohol derivatives and polyacrylamides from the viewpoints of shortening the cleaning time and reducing LPD At least one water-soluble polymer a1 selected from the group consisting of

As the polyglycerin derivative, a functional group is preferably added to the polyglycerin by an ether bond or an ester bond, more preferably by an ether bond.

The polyglycerin derivative is preferably a polyglycerin alkyl ether, a polyglycerin dialkyl ether, a polyglycerin fatty acid ester, a polyethylene oxide-added polyglycerin, a polypropylene oxide-added polyglycerin , Aminated polyglycerin and the like, and more preferably polyglycerol alkyl ether. These may be used alone or in combination of two or more.

The polyglycidol derivative is preferably a polyglycidol alkyl ether, a polyglycidol alkyl ether, a polyglycidol fatty acid ester, a polyethylene oxide-added polyglycol ether, Epoxylated polyglycidol, aminated polyglycidol, and the like. These may be used alone or in combination of two or more.

As the polyvinyl alcohol derivative, polyethylene oxide-denatured polyvinyl alcohol, sulfonic acid denatured polyvinyl alcohol, and the like are preferably used from the viewpoints of shortening the cleaning time and reducing LPD. These may be used alone or in combination of two or more.

Among them, polyglycerol, polyglycerol alkyl ether, polyglycerol dialkyl ether, polyglycerol fatty acid ester, polyethylene oxide-modified polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol, , Sulfonic acid-modified polyvinyl alcohol, and polyacrylamide, and more preferably at least one member selected from the group consisting of polyglycerin and polyglycerol alkyl ether, and more preferably at least one member selected from the group consisting of , Polyglycerol alkyl ether. The water-soluble polymer (a1) may be selected from two or more of the above. The rinse composition preferably contains both polyglycerin and polyglycerin alkyl ether from the viewpoint of shortening the cleaning time and reducing LPD. The number of carbon atoms in the hydrophobic group of the polyglycerol derivative is preferably 6 or more, more preferably 8 or more, and preferably 22 or less, more preferably 18 or less.

When the water-soluble polymer (a1) contains polyglycerin and polyglycerin alkyl ether, the mass ratio thereof (polyglycerin / polyglycerol alkyl ether) is preferably 0.5 or more, more preferably 1.0 or more , More preferably 2.0 or more, and from the same viewpoint, it is preferably 10 or less, more preferably 6.0 or less, further preferably 5.0 or less.

The weight average molecular weight of the water-soluble polymer a1 is preferably 500 or more, more preferably 700 or more, and further preferably 900 or more, from the viewpoints of shortening of the cleaning time and LPD reduction, Is preferably 1,500,000 or less, more preferably 500,000 or less, still more preferably 100,000 or less, even more preferably 25,000 or less, still more preferably 10,000 or less. The weight average molecular weight of the water-soluble polymer A can be measured by the method described in Examples.

The water-soluble polymer (a1) is preferably five or more, more preferably ten or more, more preferably 15 or more, from the viewpoints of shortening the cleaning time and reducing LPD, and from the same viewpoint, More preferably 500 or less, more preferably 200 or less, still more preferably 150 or less, or even more preferably 100 or less.

The water-soluble polymer A is a water-soluble polymer containing the water-soluble polymer a1 and a betaine structure (hereinafter, "water-soluble polymer containing a betaine structure" is abbreviated as "water-soluble polymer a2" in some cases ). ≪ / RTI >

[Water-soluble polymer containing betaine structure]

In the present invention, the betaine structure means a structure in which charges are neutralized by having static charge and negative charge in the same molecule. The betaine structure preferably has the electrostatic charge and the negative charge at positions not adjacent to each other and preferably at a position interposing one or more atoms.

As the water-soluble polymer (a2), from the viewpoint of reducing LPD, a polymer of a monomer including a betaine structure, a copolymer of a monomer containing a betaine structure and a monomer containing a hydrophobic group, a monomer containing a betaine structure and a hydroxyl group , A copolymer of a monomer containing a betaine structure and a monomer containing an oxyalkylene group, a copolymer of a monomer containing a betaine structure and a monomer containing an amino group, and a monomer containing a betaine structure And a copolymer of a monomer containing a quaternary ammonium group is preferable, and a copolymer of a monomer containing a betaine structure and a monomer containing a hydrophobic group is more preferable.

Examples of the betaine structure include sulfobetaine, carbobetaine, phosphobetaine and the like. From the viewpoint of reducing LPD, carbobetaine and phosphobetaine are more preferable, and phosphobetaine is more preferable .

The constituent unit A derived from a monomer containing a betaine structure is preferably a constituent unit represented by the following formula (1) from the viewpoint of reducing LPD.

[Chemical Formula 1]

In the above formula (1)

R ¹ to R ^{3 are the} same or different and each represents a hydrogen atom, a methyl group, or an ethyl group

R ⁴ : an alkylene group having 1 to 4 carbon atoms, or -Y ¹ -OPO ₃ ^- -Y ² -

Y ¹ and Y ² : the same or different alkylene group having 1 to 4 carbon atoms

R ⁵ and R ⁶ : same or different hydrocarbon group having 1 to 4 carbon atoms

X ¹ : O or NR ⁷

R ⁷ : a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms

X ² : a hydrocarbon group having 1 to 4 carbon atoms, -R ¹⁷ SO ₃ ^- , or -R ¹⁸ COO ^-

R ¹⁷ and R ^{18 are the} same or different and each represents an alkylene group having 1 to 4 carbon atoms.

However, X ² is, when R ⁴ is alkylene having 1 date of less than 4, -R ¹⁷ SO ₃ ^-, or -R ¹⁸ COO ^-, and, R ⁴ is -Y ¹ -OPO ₃ ^- -Y ^{2 -} il Is a hydrocarbon group having 1 to 4 carbon atoms.

Each of R ¹ and R ² is preferably a hydrogen atom from the viewpoints of the availability of the monomer, the polymerizability of the monomer, and the LPD reduction.

R ³ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoints of water availability of the monomer, polymerizability of the monomer and reduction of LPD.

X ¹ is preferably O (oxygen atom) from the viewpoints of water availability of monomers, polymerizability of monomers, and reduction of LPD.

R ⁴ is, from the viewpoint of reduction of the LPD, having 2 or 3 alkylene group, or -Y ¹ -OPO ₃ ^- -Y ^{2 -} is preferable, and an alkylene group of carbon number 2 or -Y ¹ -OPO ₃ ^{- -} Y ² - is more preferable, and -Y ¹ -OPO ₃ ^- -Y ² - is more preferable.

Y ¹ and Y ² are each preferably an alkylene group having 2 or 3 carbon atoms and more preferably an alkylene group having 2 carbon atoms from the viewpoints of the availability of the monomer, the polymerizability of the monomer and the reduction in LPD.

R ⁵ and R ⁶ are preferably a methyl group or an ethyl group, and more preferably a methyl group, from the viewpoints of the availability of the monomer, the polymerizability of the monomer, and the LPD reduction.

X ² is -R ¹⁷ SO ₃ ^- or -R ¹⁸ COO ^- when R ⁴ is an alkylene group having 1 to 4 carbon atoms and from the viewpoint of reduction of LPD, -R ¹⁸ COO ^- is preferable. X ² is a hydrocarbon group having 1 to 4 carbon atoms when R ⁴ is -Y ¹ -OPO ₃ ^- -Y ² -, and from the viewpoint of reducing LPD, a methyl group is more preferable.

The carbon number of R ¹⁷ is preferably 1 or more and 3 or less, and more preferably 2 or more and 3 or less, from the viewpoints of the availability of the monomer, the polymerizability of the monomer, and the LPD. The carbon number of R ¹⁸ is preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less, from the viewpoints of the availability of the unsaturated monomer, the polymerizability of the monomer, and the reduction of LPD.

As the constituent unit A, a constituent unit derived from at least one kind of monomer selected from sulfobetaine methacrylate, methacryloyloxyethylphosphorylcholine, and carboxybetaine methacrylate is preferable from the viewpoint of reducing LPD More preferably a structural unit derived from at least one monomer selected from methacryloyloxyethylphosphoryl choline and carboxybetaine methacrylate, and a constitutional unit derived from methacryloyloxyethylphosphoryl choline Unit is more preferable.

 Wherein the water-soluble polymer (a2) is at least one monomer selected from monomers including a hydrophobic group, monomers including a hydroxyl group, monomers including an oxyalkylene group, monomers including an amino group, and monomers including a quaternary ammonium group (hereinafter, (Hereinafter sometimes abbreviated as " monomer B ") and a copolymer of a monomer containing a betaine structure, the constituent unit B derived from monomer B is preferably a monomer having a structure represented by the following formula 2) is preferable.

(2)

However, in the formula (2)

R ⁸ to R ^{10 are the} same or different and each represents a hydrogen atom, a methyl group or an ethyl group

X ³ : O or NR ¹⁹

R ¹⁹ : a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms

R ¹¹ : an alkylene group having 1 to 22 carbon atoms (provided that the hydrogen atom of the alkylene group may be substituted with a hydroxyl group) or - (AO) _m - (wherein AO is an alkyleneoxy group having 2 to 4 carbon atoms and m is an average addition mole number of 1 to 150.)

X ⁴ : a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms (provided that the hydrogen atom of the hydrocarbon group may be substituted with a hydroxyl group), a hydroxyl group, N ⁺ R ¹² R ¹³ R ¹⁴ or NR ¹⁵ R ¹⁶

R ¹² to R ^{16 are the} same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

Each of R ⁸ and R ⁹ is preferably a hydrogen atom from the viewpoints of the availability of the monomer, the polymerizability of the monomer, and the LPD reduction.

R ¹⁰ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoints of the availability of the monomer, the polymerizability of the monomer and the reduction of LPD.

X ³ is preferably O from the viewpoints of water availability of the monomer, polymerizability of the monomer, and reduction of LPD.

When X ⁴ is a hydrogen atom, the number of carbon atoms of the alkylene group represented by R ¹¹ is preferably 3 or more, more preferably 4 or more, and more preferably 6 or more, from the viewpoints of the availability of the monomer, the polymerizability of the monomer, More preferably not more than 18, more preferably not more than 12, and m is preferably not less than 2 but not more than 30 from the same viewpoint.

When X ⁴ is a hydrocarbon group of 1 to 4 carbon atoms, R ¹¹ is preferably - (AO) _m - from the viewpoints of water availability of the monomer, polymerizability of the monomer, and LPD reduction, 90 or less is preferable.

AO is preferably selected from an ethyleneoxy group (EO), which is an alkyleneoxy group having 2 carbon atoms, and a propyleneoxy group (PO), which is an alkyleneoxy group having 3 carbon atoms, in view of the availability of monomers, the polymerizability of monomers and the reduction of LPD Is preferably composed of at least one alkyleneoxy group, and more preferably composed of EO. When - (AO) _m - contains two or more alkyleneoxy groups having different carbon numbers, the arrangement of the various alkyleneoxy groups may be a block or random, preferably a block.

When X ⁴ is a hydroxyl group, N ⁺ R ¹² R ¹³ R ¹⁴ or NR ¹⁵ R ¹⁶ , R ¹¹ is preferably an alkylene group having 1 to 22 carbon atoms, more preferably an alkylene group having 1 to 22 carbon atoms (Provided that the hydrogen atom of the hydrocarbon group may be substituted with a hydroxyl group), and the number of carbon atoms of the alkylene group is preferably 2 or more, more preferably 3 or less, and more preferably 2 or less desirable.

X ⁴ is preferably a hydrogen atom, a methyl group, a hydroxyl group, or N ⁺ R ¹² R ¹³ R ¹⁴ , and R ¹² to R ¹⁴ are preferably a hydrogen atom, a methyl group, a hydroxyl group or the like from the viewpoint of water availability of a monomer, , A methyl group or an ethyl group is preferable, and a methyl group is more preferable.

The constituent unit B is preferably an unsaturated monomer having a hydrophilic group (the hydrogen atom of the hydrophilic group may be substituted with a hydroxyl group) such as alkyl methacrylate, a quaternary A constituent unit derived from at least one kind of monomer selected from an unsaturated monomer having a cationic group such as methacrylate having an ammonium cation and an unsaturated monomer having a non-ionic group such as methacrylate having an ethyleneoxy group is preferable , And alkyl methacrylate (the hydrogen atom of the hydrophilic group may be substituted with a hydroxyl group) is more preferable.

Examples of the structural unit B include butyl methacrylate (BMA), 2-ethylhexyl methacrylate (EHMA), lauryl methacrylate (LMA), stearyl methacrylate (SMA), methacryloyloxyethyldimethylethyl (Meth) acrylates such as methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, (Meth) acrylate monomer derived from at least one monomer selected from glycol methacrylate (PEGMA), methoxy polypropylene glycol methacrylate (MPPGMA), polypropylene glycol methacrylate (PPGMA) and hydroxyethyl methacrylate More preferably a constituent unit, and more preferably a constituent unit derived from at least one kind of monomer selected from BMA and LMA.

(Molar ratio of the constituent unit A to the constituent unit B)

The molar ratio (constituent unit A / constituent unit B) of the constituent unit A and the constituent unit B in the water-soluble polymer a2 is preferably 10/90 or more, more preferably 20/80 or more, More preferably 30/70 or more, and from the same viewpoint, preferably 98/2 or less, and more preferably 95/5 or less.

(Structural units other than the structural units A and B)

The water-soluble polymer (a2) may contain a constituent unit other than the constituent unit (A) and the constituent unit (B) within the range not hindering the effect of the present invention. As the constituent unit other than the constituent unit A and the constituent unit B, a constituent unit derived from a hydrophobic unsaturated monomer such as styrene is preferable.

The content of the constituent units other than the constituent unit A and the constituent unit B in the water-soluble polymer a2 is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, 0.05% by mass or less. The content of the constituent units other than the constituent unit A and the constituent unit B in the water-soluble polymer a2 may be 0 mass%.

The total content of the constituent unit A and the constituent unit B in the water-soluble polymer a2 is preferably 99% by mass or more, more preferably 99.5% by mass or more, still more preferably 99.9% by mass or more, still more preferably 99.95% % Or more, and may be 100% by mass.

The weight average molecular weight of the water-soluble polymer (a2) is preferably at least 0.1 million, more preferably at least 0.3 million, more preferably at least 0.5 million from the viewpoint of LPD reduction, and the solubility of the water- , It is preferably 1.5 million or less, more preferably 1.2 million or less, and even more preferably 1 million or less.

The content of the water-soluble polymer a2 in the rinse composition of the present invention is preferably 0.00001% by mass or more, more preferably 0.00005% by mass or more, still more preferably 0.0001% by mass or more from the viewpoint of reducing LPD, And from the viewpoint of LPD reduction, 10 mass% or less is preferable, 5 mass% or less is more preferable, and 1 mass% or less is more preferable.

The mass ratio (water-soluble polymer a1 / water-soluble polymer a2) of the water-soluble polymer a1 to the water-soluble polymer a2 in the rinse composition of the present invention is preferably 0.5 or more, more preferably 1 or more, More preferably 2 or more, and from the viewpoint of reducing LPD, 500 or less is preferable, 200 or less is more preferable, and 100 or less is more preferable.

[Water medium]

Examples of the aqueous medium included in the rinse composition of the present invention include water such as ion-exchanged water and ultrapure water, or a mixed medium of water and a solvent. Examples of the solvent include polyhydric alcohols having 2 to 4 carbon atoms, and glycerin or propylene glycol is preferable. As the water in the water-based medium, ion-exchanged water or ultrapure water is preferable, and ultrapure water is more preferable. When the aqueous medium is a mixed medium of water and a solvent, the ratio of water to the total amount of the mixed medium is preferably 90 mass% or more, more preferably 92 mass% or more, and more preferably 95 mass% or more desirable.

The content of the aqueous medium in the rinsing composition of the present invention is preferably the residual amount of the water-soluble polymer A, the basic compound to be described later, which is added as required, and other optional components described below.

[Optional ingredients (supplements)]

The rinse composition of the present invention may further contain at least one selected from the group consisting of a pH adjuster, an antiseptic, an alcohol, a chelating agent, an anionic surfactant, and a nonionic surfactant, May be included.

[pH adjusting agent]

Examples of the pH adjuster include a basic compound, an acidic compound, and a salt thereof. The salt of the acidic compound is preferably at least one member selected from an alkali metal salt, an ammonium salt and an amine salt, more preferably an ammonium salt. The counter ion in the case where the basic compound takes the form of a salt is preferably at least one selected from a hydroxide ion, a chloride ion and an iodide ion, more preferably at least one selected from a hydroxide ion and a chloride ion .

(Basic compound)

Examples of the basic compound include sodium hydroxide, potassium hydroxide, ammonia, ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monoethanolamine , Diethanolamine, triethanolamine, N-methylethanolamine, N-methyl-N, N-diethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, (2-aminoethyl) amine, N- (p-aminoethyl) ethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethylenediamine, hexamethylenediamine, piperazine hexahydrate, Piperazine, N-methylpiperazine, diethylenetriamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide. Two or more of these basic compounds may be used. As the basic compound, ammonia is more preferable from the viewpoints of both the reduction of haze and the reduction of LPD of the silicon wafer and the improvement of the storage stability of the rinse composition.

(Acidic compound)

Examples of the acidic compound include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid, and organic acids such as acetic acid, oxalic acid, succinic acid, glycolic acid, malic acid, citric acid or benzoic acid.

[antiseptic]

Examples of the preservative include phenoxyethanol, benzalkonium chloride, benzethonium chloride, 1,2-benzisothiazolin-3-one, (5-chloro-) , Or hypochlorite, and the like.

[Alcohols]

Examples of the alcohols include methanol, ethanol, propanol, butanol, isopropyl alcohol, 2-methyl-2-propanol, ethylene glycol, propylene glycol, polyethylene glycol and glycerin. The content of the alcohol in the rinse composition of the present invention is preferably 0.01% by mass to 10% by mass.

[Chelating agent]

Examples of the chelating agent include 1-hydroxyethane 1,1-diphosphonic acid, ethylenediaminetetraacetic acid, ethylenediaminetetraacetate, nitrilotriacetic acid, sodium nitrilotriacetate, ammonium nitrilotriacetate, hydroxyethylethylenediamine 3-acetic acid, hydroxyethylethylenediamine triacetate, triethylenetetramine-6-acetic acid, and triethylenetetramine-6-acetic acid sodium. The content of the chelating agent in the rinsing composition of the present invention is preferably 0.001 to 10% by mass.

[Anionic surfactant]

Examples of the anionic surfactant include carboxylic acid salts such as fatty acid soap and alkyl ether carboxylate salts, sulfonic acid salts such as alkylbenzenesulfonic acid salts and alkylnaphthalenesulfonic acid salts, higher alcohol sulfuric acid ester salts and alkyl ether sulfates Sulfuric acid ester salts, phosphoric acid ester salts such as alkyl phosphate esters and the like.

[Nonionic surfactant]

Examples of the nonionic surfactant include polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, poly Polyethylene glycol type such as oxyalkylene (hardened) castor oil, polyvalent alcohol type such as sucrose fatty acid ester and alkyl glycoside, and fatty acid alkanolamide.

The pH of the rinse composition of the present invention at 25 캜 is preferably 2 or more, more preferably 2.5 or more, and more preferably 3.0 or more, from the viewpoints of shortening the cleaning time, reducing LPD and improving the storage stability of the rinse composition And from the same viewpoint, 12 or less is preferable, 11.5 or less is more preferable, and 11.0 or less is more preferable. The pH can be adjusted by appropriately adding a pH adjuster, if necessary. Here, the pH at 25 占 폚 can be measured using a pH meter (HM-30G, Toa Radio Co., Ltd.), and is a value one minute after immersing the electrode in the rinse composition.

The content of each ingredient described above is the content at the time of use, but the rinse composition of the present invention may be stored and supplied in a concentrated state within a range in which the storage stability is not impaired. In this case, production and transportation costs can be further reduced. The concentrated liquid may be appropriately diluted with the above-mentioned aqueous medium if necessary. The concentration ratio is not particularly limited as long as the concentration at the time of polishing after dilution can be secured, but is preferably 2 times or more, more preferably 10 times or more, from the viewpoint of further lowering the production and transportation costs More preferably 20 times or more, even more preferably 30 times or more.

When the rinsing composition of the present invention is the concentrate, the content of the water-soluble polymer A in the concentrate is preferably 0.02% by mass or more, more preferably 0.1% by mass or more, More preferably not less than 0.5% by mass, still more preferably not less than 1.0% by mass, still more preferably not less than 1.5% by mass, and from the viewpoint of improvement of the storage stability, preferably not more than 20% Is not more than 15 mass%, more preferably not more than 10 mass%, still more preferably not more than 7.0 mass%.

When the rinse composition of the present invention is the concentrate, the pH of the concentrate at 25 캜 is preferably 1.5 or more, more preferably 1.7 or more, further preferably 2.0 or more, and preferably 12.5 Or less, more preferably 12.0 or less, and still more preferably 11.5 or less.

[Method for producing rinse composition]

The rinse composition of the present invention can be produced, for example, by a manufacturing method including a step of blending water-soluble polymer A with an aqueous medium and optional components in a known manner. As used herein, the phrase " blending " includes mixing water-soluble polymer A and optional components, if necessary, simultaneously or sequentially with an aqueous medium. There is no limitation on the mixing order of the respective components.

The mixing can be carried out using, for example, a mixer such as a homomixer, a homogenizer, an ultrasonic disperser, and a wet ball mill. The blending amount of each component in the method of producing the rinsing composition of the present embodiment may be the same as the content of each component of the rinsing composition described above.

[Method of Manufacturing Semiconductor Substrate]

The rinsing composition of the present invention is used to remove residues remaining on the surface of a silicon wafer after polishing using abrasive liquid compositions containing abrasive grains and water-soluble polymer B. An example of a method for producing a semiconductor substrate of the present invention is a polishing method for polishing a silicon wafer to be polished (also referred to as a " polishing substrate ") using an abrasive liquid composition including abrasive grains, A rinsing step of rinsing with the rinsing composition of the present invention and a cleaning step of cleaning the silicon wafer rinsed in the rinsing step (also referred to as " rinsing silicon wafer "). An example of a semiconductor substrate is, for example, a silicon wafer, and an example of a method of manufacturing a semiconductor substrate of the present invention is a method of manufacturing a silicon wafer. Another example of the manufacturing method of the semiconductor substrate of the present invention is a manufacturing method of a semiconductor substrate including a step of manufacturing a silicon wafer by the manufacturing method of the silicon wafer of the present invention, A polishing step of polishing the silicon wafer, a rinsing step of rinsing the polished silicon wafer using the rinsing composition of the present invention, and a cleaning step of cleaning the rinsed silicon wafer.

The polishing step includes a lapping (rough polishing) step of planarizing a silicon wafer obtained by slicing a silicon single crystal ingot into a thin disk-like shape, and a finish polishing step of polishing the surface of the silicon wafer after etching the lapped silicon wafer .

In the polishing step, for example, the polishing liquid composition is supplied between the polishing target silicon wafer and the pad, and the pad is moved relative to the polishing target silicon wafer in a state where the polishing target silicon wafer and the pad are in contact with each other. The polishing conditions such as the number of revolutions of the pad, the number of revolutions of the substrate to be polished, the polishing load set on the polishing apparatus having the pad, the feeding rate of the polishing liquid composition, and the polishing time may be the same as conventionally known polishing conditions.

It is preferable that the abrasive composition used in the polishing step includes silica particles as the abrasive grains and contains the water-soluble polymer B from the viewpoints of, for example, improvement in the polishing rate and reduction in haze of the silicon wafer.

In the rinsing step, for example, a rinsing composition is supplied between the silicon wafer and the pad after polishing, and the pad is polished and then moved relative to the silicon wafer in a state where the pad is in contact with the silicon wafer after polishing. The rinsing treatment in the rinsing step can be carried out using a polishing apparatus used in the polishing step. The number of revolutions of the pad, the number of revolutions of the silicon wafer after polishing, the load set in the polishing apparatus equipped with the pad, the feeding rate of the rinsing composition, and the like may be the same as or different from the corresponding conditions in the polishing step. The rinsing time is preferably not less than 1 second, more preferably not less than 3 seconds from the viewpoint of inhibition of adhesion of abrasive grains, preferably not more than 60 seconds, more preferably not more than 30 seconds, from the viewpoint of productivity improvement. Here, the rinse time means the time during which the rinse composition is supplied.

The rinsing step may include a water rinse treatment using water as a rinsing liquid before the rinsing treatment using the rinsing composition of the present invention. The water rinse treatment time is preferably 2 seconds or more and 30 seconds or less.

The pad used in the rinsing step may be the same as the pad used in the polishing process, or may be any of nonwoven fabric type, suede type, and the like. The pad used in the polishing step may be used in the rinsing step as it is without being exchanged. In this case, the abrasive of the polishing liquid composition may be slightly contained in the pad. The rinsing step may be performed on the silicon wafer mounted in the polishing apparatus immediately after the polishing step.

The temperature of the rinsing composition used in the rinsing step is preferably 5 to 60 ° C.

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

In the cleaning step, for example, after the rinsing, the silicon wafer is immersed in the cleaning agent or, after rinsing, the cleaning agent is injected onto the surface of the silicon wafer to be cleaned. As the cleaning agent, conventionally known cleaning agents may be used. For example, an aqueous solution containing ozone, an aqueous solution containing ammonium hydrogen fluoride, and the like can be given. The cleaning time may be set according to the cleaning method.

The polishing liquid composition used in the polishing step includes, for example, silica particles, a water-soluble polymer B and a nitrogen-basic compound and an aqueous medium. The abrasive composition preferably includes the water-soluble polymer B from the viewpoint of both improvement in polishing rate and reduction in LPD.

[Water-soluble polymer B]

(1) Water-soluble polymer B

The water-soluble polymer B is a water-soluble polymer having a difference (z - z ₀ ) between the zeta potential z of the aqueous dispersion s and the zeta potential z ₀ of the aqueous dispersion s ₀ is not less than 15.. Here, the aqueous dispersion s is composed of the water-soluble polymer B, silica particles, water and, if necessary, hydrochloric acid or ammonia, and the concentration of the water-soluble polymer B is 0.01% by mass, the concentration of the silica particles is 0.1% by mass, containing water-soluble polymer having a pH of 10.0. The aqueous dispersion s ₀ is a silica aqueous dispersion comprising silica particles, water and, if necessary, hydrochloric acid or ammonia, and the concentration of the silica particles is 0.1% by mass and the pH at 25 캜 is 10.0. The zeta potential z, z ₀ can be measured by the method described in the examples. When the water-soluble polymer B is composed of two or more water-soluble polymers, the mixture of two or more water-soluble polymers B has a zeta potential difference (z - z ₀ ) of 15 ㎷ or more.

The zeta potential difference (z - z ₀ ) is preferably not less than 15,, preferably not less than 25,, more preferably not less than 30 ㎷, from the viewpoint of improving the polishing rate, Or less, more preferably 46 ㎷ or less.

The zeta potential z ₀ of the aqueous dispersion s ₀ is a predetermined value within a range of, for example, -50 ㎷ to -70 ㎷. As an example thereof, the zeta potential z ₀ of the aqueous dispersion s ₀ is adjusted by using a silica stock solution (PL- Zeta potential of the aqueous dispersion z ₀ (for example, -61 ㎷).

And a secondary particle diameter of the silica particles in the aqueous dispersion s D, ratio (D / D ₀₎ of the secondary particle diameter D ₀ of the silica particles in the aqueous dispersion s ₀ is, in view of improving the polishing rate, preferably at least 1.10 , More preferably not less than 1.15, further preferably not less than 1.30, and preferably not more than 1.60 from the viewpoint of reducing LPD.

Dispersion s ₀ 2 primary particle diameter D ₀ of the silica particles in, for example, a predetermined value in the range of 64 ~ 73 ㎚, preferably a predetermined value in the range of 66 ~ 69 ㎚, as an example, of silica (For example, 67.7 nm) of the silica particles in the aqueous dispersion s ₀ containing the undiluted solution ("PL-3" manufactured by Fuso Chemical Co., Ltd.) as a source of the silica particles.

The water-soluble polymer B is preferably at least one selected from the group consisting of a polysaccharide, an alkyl acrylamide-based polymer, polyvinyl alcohol (PVA), and a polyvinyl alcohol derivative (except an anion-modified polyvinyl alcohol) . As the polysaccharide, hydroxyethyl cellulose (HEC) is preferable. As the alkyl acrylamide-based polymer, poly (hydroxy) alkyl acrylamide and polyalkyl acrylamide are preferable, and polyhydroxyethylacrylamide (pHEAA) is more preferable. As the polyvinyl alcohol derivative, polyvinyl alcohol, polyethylene glycol, graft copolymer (PEG-g-PVA), and polyethylene oxide-modified polyvinyl alcohol are preferable. Among these, water-soluble polymer B is preferably selected from the group consisting of HEC, poly (hydroxy) alkyl acrylamide, PVA, PEG-g-PVA, and polyethylene oxide-modified polyvinyl Alcohol, and more preferably at least one selected from the group consisting of HEC, pHEAA, and PVA, and more preferably at least one selected from HEC and pHEAA , And even more preferably HEC.

The weight average molecular weight of the water-soluble polymer B is preferably 10,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more, from the viewpoint of both improvement in polishing rate and reduction in LPD, Preferably 5,000,000 or less, more preferably 3,000,000 or less, and still more preferably 1,000,000 or less. The weight average molecular weight of the water-soluble polymer B can be measured by the method described in the Examples.

The content of the water-soluble polymer B in the polishing liquid composition is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, still more preferably 0.005% by mass or more from the viewpoint of improvement in polishing rate, From the same viewpoint, it is preferably 1.0 mass% or less, more preferably 0.5 mass% or less, and further preferably 0.1 mass% or less.

When the water-soluble polymer A contained in the rinsing composition used in the rinsing process is at least one selected from the group consisting of polyglycerin and polyglycerin derivatives, the water-soluble polymer B contained in the polishing liquid composition used in the polishing step has an improved polishing rate And HEC and poly (hydroxy) alkyl acrylamides are preferable from the viewpoint of compatibility with LPD reduction. When the water-soluble polymer A contained in the rinsing composition used in the rinsing step is a polyglycerin derivative, the water-soluble polymer B contained in the polishing liquid composition used in the polishing step is preferably HEC. In this case, the polyglycerin derivative preferably contains a polyglycerol alkyl ether, and more preferably a polyglycerol alkyl ether.

[Silica particles]

From the viewpoint of improving the surface smoothness of the silicon wafer, the silica particles contained in the polishing liquid composition are more preferably colloidal silica, and from the viewpoint of preventing the contamination of the silicon wafer by alkali metals or alkaline earth metals, It is preferably one obtained from the degradation product. The average primary particle diameter of the silica particles contained in the polishing liquid composition is preferably 5 nm or more, more preferably 10 nm or more, from the viewpoint of securing a high polishing rate, and from the viewpoint of reducing LPD, Is 50 nm or less, and more preferably 45 nm or less. The average primary particle diameter of the silica particles can be calculated using the specific surface area S (m 2 / g) calculated by the BET (nitrogen adsorption) method.

The degree of association of the silica particles is preferably 1.1 or more and 3.0 or less, more preferably 1.8 or more and 2.5 or less from the viewpoint of securing a high polishing rate and reducing LPD. The association degree of the silica particles is a coefficient indicating the shape of the silica particles and is calculated by the following formula. The average secondary particle diameter is a value measured by the dynamic light scattering method, and can be measured using, for example, the apparatus described in the embodiment.

Association degree = average secondary particle diameter / average primary particle diameter

The content of the silica particles contained in the polishing liquid composition is preferably not less than 0.05% by mass, more preferably not less than 0.1% by mass, from the viewpoint of securing a high polishing rate, and is economical, Is preferably 10% by mass or less, and more preferably 7.5% by mass or less from the viewpoints of suppressing aggregation of silica particles and improving dispersion stability.

[Nitrogen Basic Compound]

From the viewpoints of securing a high polishing rate and reducing surface roughness (haze) and surface defects (LPD), the nitrogen-containing basic compound contained in the polishing liquid composition is preferably at least one kind of nitrogen-containing compound selected from amine compounds and ammonium compounds Basic compounds such as ammonia, ammonium hydroxide, ammonium carbonate, ammonium hydrogencarbonate, dimethylamine, trimethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine , N, N-diethylethanolamine, N, N-dibutylethanolamine, N- (? -Aminoethyl) ethanolamine, mono But are not limited to, isopropanolamine, diisopropanolamine, triisopropanolamine, ethylenediamine, hexamethylenediamine, piperazine hexahydrate, piperazine anhydride, 1- (2-aminoethyl) piperazine, N-methylpiperazine, diethylenetriamine, Hydroxide Tra and methyl ammonium, and hydroxy amine. Among them, ammonia, a mixture of ammonia and hydroxyamine is preferable, and ammonia is more preferable.

The content of the nitrogen-containing basic compound contained in the polishing liquid composition is preferably 0.001% by mass or more, more preferably 0.001% by mass or more from the viewpoints of reduction in surface roughness (haze) and surface defect (LPD) Preferably not less than 1% by mass, more preferably not more than 0.5% by mass, from the viewpoint of reducing the surface roughness (haze) and the surface defect (LPD) of the silicon wafer.

[Water medium]

The aqueous medium contained in the polishing liquid composition may be the same as the aqueous medium contained in the rinse composition of the present invention. The content of the aqueous medium in the polishing liquid composition may be, for example, residual silica particles other than water-soluble polymer B, nitrogen-containing basic compound, and optional components to be described later.

The pH of the polishing liquid composition at 25 캜 is preferably 8 or more, more preferably 9 or more, further preferably 10 or more from the viewpoint of securing a high polishing rate, and from the viewpoint of safety, Is 12 or less, more preferably 11 or less. The pH can be adjusted by appropriately adding a nitrogen-containing basic compound and / or a pH adjuster. Here, the pH at 25 占 폚 can be measured using a pH meter (HM-30G, Toa Denshi Kogyo Co., Ltd.), and is a value one minute after immersion in the polishing liquid composition of the electrode.

The abrasive liquid composition can be produced, for example, by a manufacturing method comprising a step of blending silica particles, a water-soluble polymer B, a water-based medium and a nitrogen-basic compound, and optionally an optional component in a known manner. Examples of optional components include at least one optional component selected from water-soluble polymers other than the water-soluble polymer B, pH adjusters, preservatives, alcohols, chelating agents and nonionic surfactants.

The method of manufacturing a semiconductor substrate of the present invention may further include a step of forming an element isolation film, a step of planarizing an interlayer insulating film, a step of forming a metal wiring, and the like, in addition to the step of manufacturing a silicon wafer.

[Rinse method]

The rinsing method of a silicon wafer of the present invention (hereinafter also referred to as " rinsing method of the present invention ") includes a rinsing step of rinsing a silicon wafer after polishing using the rinsing composition of the present invention. The rinsing step in the rinsing method of the present invention can be carried out in the same manner as in the rinsing step in the method for producing a silicon wafer of the present invention and the method for producing a semiconductor substrate of the present invention. In the rinsing method of the present invention, since the rinsing composition of the present invention is used in the rinsing step, the residual amount of the abrasive grains on the silicon wafer after polishing can be remarkably reduced and further the cohesion of the abrasive grains can be suppressed. It is possible to shorten the cleaning time and the LPD of the silicon wafer to be implemented.

The present invention also relates to the following composition, manufacturing method and the like.

[1] A rinse composition for a silicon wafer comprising a water-soluble polymer and an aqueous medium,

The water-

Wherein the water-soluble polymer is composed of the water-soluble polymer, silica particles, water and, if necessary, hydrochloric acid or ammonia, the concentration of the water-soluble polymer is 0.1 mass%, the concentration of the silica particles is 0.1 mass% Containing zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide and zirconium oxide. Wherein the difference (Z - Z ₀ ) between the zeta potentials Z ₀ of the water dispersion (water dispersion S ₀ ) is 25 ㎷ or less.

[2] A rinse composition for a silicon wafer comprising a water-soluble polymer and an aqueous medium,

Wherein the water-soluble polymer is at least one selected from the group consisting of polyglycerin, polyglycerin derivatives, polyglycidol, polyglycidol derivatives, polyvinyl alcohol derivatives, and polyacrylamides. / RTI >

[3] The rinse composition for a silicon wafer according to [1], wherein the difference (Z - Z ₀ ) is preferably 15 ㎷ or less, more preferably 9 ㎷ or less, and further preferably 7 ㎷ or less.

[4] The water-soluble polymer according to [

And a secondary particle diameter of the silica particles in aqueous dispersion S wherein d, the ratio (d / d ₀₎ of the secondary particle diameter of the silica particles in the aqueous dispersion S ₀ d _0, preferably 1.35 or less, more preferably 1.17 or less , More preferably not more than 1.10, even more preferably not more than 1.08, and preferably not less than 1.00, more preferably not less than 1.02, further preferably not less than 1.04, even more preferably not less than 1.05, A rinse composition for a silicon wafer according to the above [1] or [3], which is a polymer.

[5] The water-soluble polymer according to any one of [1] to [5], wherein the water-soluble polymer is at least one selected from the group consisting of polyglycerol, polyglycerol derivative, polyglycidol, polyglycidol derivative, polyvinyl alcohol derivative, and polyacrylamide The rinse composition for a silicon wafer according to any one of [1], [3] and [4].

[6] The polyglycerol derivative is preferably a polyglycerin having a functional group added by an ether bond or an ester bond, more preferably a polyglycerin having a functional group added by an ether bond. [2] or [ 5]. ≪ / RTI >

[7] The rinse composition for a silicon wafer according to the above [5], wherein the polyglycerin derivative is preferably an alkyl ether of polyglycerin.

[8] The water-soluble polymer is preferably selected from the group consisting of polyglycerin, polyglycerin alkyl ether, polyglycerin dialkyl ether, polyglycerin fatty acid ester, polyethylene oxide denatured polyvinyl alcohol, sulfonic acid denatured polyvinyl alcohol and polyacrylamide The rinse composition for a silicon wafer according to any one of the above [1] to [4], wherein the rinse composition is at least one selected from the group consisting of polyglycerol alkyl ethers, and more preferably polyglycerol alkyl ethers.

[9] The rinse composition for a silicon wafer according to any one of [1] to [4], wherein the water-soluble polymer preferably contains both polyglycerin and polyglycerin alkyl ether.

[10] The polyglycerol derivative according to any one of [2], [5] to [5], wherein the number of carbon atoms in the hydrophobic group is preferably 6 or more, more preferably 8 or more, and preferably 22 or less, and more preferably 18 or less. The rinse composition for a silicon wafer according to any one of [7] to [7].

[11] The mass ratio (polyglycerin / polyglycerol alkyl ether) is preferably 0.5 or more, more preferably 1.0 or more, further preferably 2.0 or more, and preferably 10 or less, more preferably 6.0 or less , More preferably 5.0 or less, based on the total weight of the rinse composition.

The weight average molecular weight of the water-soluble polymer is preferably 500 or more, more preferably 700 or more, further preferably 900 or more, and preferably 1,500,000 or less, more preferably 500,000 or less The rinse composition for a silicon wafer according to any one of [2], [5] to [11], wherein the rinse composition is 100,000 or less, more preferably 25,000 or less, and even more preferably 10,000 or less.

[13] The water-soluble polymer is preferably five or more, more preferably ten or more, more preferably 15 or more, and preferably 5,000 or less, more preferably 500 or less The rinse composition for a silicon wafer according to any one of [2], [5] to [12], wherein the rinse composition is at most 200 moles, more preferably at most 150 moles, even more preferably at most 100 moles.

The content of the water-soluble polymer in the rinsing composition is preferably 0.001% by mass or more, more preferably 0.015% by mass or more, still more preferably 0.020% by mass or more, still more preferably 0.025% by mass or more, , More preferably not less than 0.03 mass%, and preferably not more than 1.0 mass%, more preferably not more than 0.7 mass%, further preferably not more than 0.4 mass%, even more preferably not more than 0.1 mass% The rinse composition for a silicon wafer according to any one of the above [1] to [13], wherein the rinse composition is 0.08 mass% or less, more preferably 0.08 mass% or less.

[15] The water-soluble polymer according to any one of [1] to [6], wherein the water-soluble polymer is at least one water-soluble polymer a1 selected from the group consisting of polyglycerol, polyglycerol derivatives, polyglycidol, polyglycidol derivatives, polyvinyl alcohol derivatives, The rinse composition for a silicon wafer according to [1], which is a mixture of a water-soluble polymer a2 containing a betaine structure.

[16] The rinse composition for a silicon wafer according to the above-mentioned [15], wherein the water-soluble polymer is a mixture of a polyglycerol alkyl ether and a water-soluble polymer a2 containing a betaine structure.

The difference (Z-Z ₀ ) in the above-mentioned [15] or [16] is preferably 15 ㎷ or less, more preferably 12 ㎷ or less, and further preferably 9 ㎷ or less. Rinse composition for a wafer.

[18] The water-

And a secondary particle diameter of the silica particles in aqueous dispersion S wherein d, the ratio (d / d ₀₎ of the secondary particle diameter of the silica particles in the aqueous dispersion S ₀ d _0, preferably 1.35 or less, more preferably 1.34 or less , More preferably not more than 1.33, even more preferably not more than 1.32, and preferably not less than 1.00, more preferably not less than 1.25, more preferably not less than 1.30, still more preferably not less than 1.31 The rinse composition for a silicon wafer according to any one of the above [15] to [17], which is a polymer.

The content of the water-soluble polymer (a2) in the rinsing composition is preferably 0.00001% by mass or more, more preferably 0.00005% by mass or more, further preferably 0.0001% by mass or more, The rinse composition for a silicon wafer according to any one of the above-mentioned [15] to [18], wherein the amount is 10 mass% or less, more preferably 5 mass% or less, further preferably 1 mass% or less.

[20] The mass ratio (water-soluble polymer a1 / water-soluble polymer a2) of the water-soluble polymer a1 and the water-soluble polymer a2 is preferably 0.5 or more, more preferably 1 or more, further preferably 2 or more, The rinse composition for a silicon wafer according to any one of the above-mentioned [15] to [19], wherein the ratio is 500 or less, more preferably 200 or less, and further preferably 100 or less.

[21] The rinse composition for a silicon wafer according to any one of [15] to [20], wherein the water-soluble polymer a2 comprises a constituent unit A represented by the following formula (1).

(3)

However, in the above formula (1)

R ¹ to R ^{3 are the} same or different and each represents a hydrogen atom, a methyl group, or an ethyl group

R ⁴ : an alkylene group having 1 to 4 carbon atoms, or -Y ¹ -OPO ₃ ^- -Y ² -

Y ¹ and Y ² : the same or different alkylene group having 1 to 4 carbon atoms

R ⁵ and R ⁶ : same or different hydrocarbon group having 1 to 4 carbon atoms

X ¹ : O or NR ⁷

R ⁷ : a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms

X ² : a hydrocarbon group having 1 to 4 carbon atoms, -R ¹⁷ SO ₃ ^- , or -R ¹⁸ COO ^-

R ¹⁷ and R ^{18 are the} same or different and each represents an alkylene group having 1 to 4 carbon atoms.

However, X ² is, when R ⁴ is alkylene having 1 date of less than 4, -R ¹⁷ SO ₃ ^-, or -R ¹⁸ COO ^-, and, R ⁴ is -Y ¹ -OPO ₃ ^- -Y ^{2 -} il Is a hydrocarbon group having 1 to 4 carbon atoms.

[22] The rinse composition for a silicon wafer according to the above-mentioned [21], wherein the water-soluble polymer a2 comprises a constituent unit B represented by the following formula (2).

[Chemical Formula 4]

However, in the formula (2)

R ⁸ to R ^{10 are the} same or different and each represents a hydrogen atom, a methyl group or an ethyl group

X ³ : O or NR ¹⁹

R ¹⁹ : a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms

R ¹¹ : an alkylene group having 1 to 22 carbon atoms (provided that the hydrogen atom of the alkylene group may be substituted with a hydroxyl group) or - (AO) _m - (wherein AO is an alkyleneoxy group having 2 to 4 carbon atoms and m is an average addition mole number of 1 to 150.)

X ⁴ : a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms (provided that the hydrogen atom of the hydrocarbon group may be substituted with a hydroxyl group), a hydroxyl group, N ⁺ R ¹² R ¹³ R ¹⁴ or NR ¹⁵ R ¹⁶

R ¹² to R ^{16 are the} same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

The molar ratio (constituent unit A / constituent unit B) of the constituent unit A and the constituent unit B in the water-soluble polymer a2 is preferably 10/90 or more, more preferably 20/80 or more, The rinse composition for a silicon wafer according to the above [22], wherein the rinse composition is preferably 30/70 or more, and preferably 98/2 or less, more preferably 95/5 or less.

[24] The rinse composition for a silicon wafer according to any one of [1] to [23], further comprising a basic compound.

The pH of the rinse composition at 25 ° C is preferably 2 or more, more preferably 2.5 or more, still more preferably 3.0 or more, and preferably 12 or less, more preferably 11.5 The rinse composition for a silicon wafer according to any one of the above [1] to [24], wherein the rinse composition is at most 11.0, more preferably at most 11.0.

The rinsing composition for a silicon wafer is a rinsing composition for a silicon wafer used for a silicon wafer polished using a polishing liquid composition comprising silica particles and a water-soluble polymer,

Any one of the above-mentioned [1], [3] to [25], wherein the silica particles used for preparing the aqueous dispersion S and the aqueous dispersion S ₀ are the same as the silica particles contained in the polishing liquid composition A rinse composition for a silicon wafer.

[27] A rinsing method of a silicon wafer, which comprises rinsing a polished silicon wafer using the rinsing composition according to any one of [1] to [26].

[28] A method for manufacturing a semiconductor substrate, which comprises rinsing a polished silicon wafer with the rinsing composition according to any one of [1] to [26].

A polishing process for polishing a silicon wafer to be polished using a polishing liquid composition comprising silica particles and a water-soluble polymer,

A rinsing step of rinsing the polished silicon wafer with the rinsing composition according to any one of [1] to [26]

And a cleaning step of cleaning the rinsed silicon wafer,

Wherein the silica particles used for preparing the aqueous dispersion S and the aqueous dispersion S ₀ are the same as the silica particles contained in the polishing liquid composition.

The polishing step is preferably a polishing step in which the silicon wafer obtained by slicing the silicon single crystal ingot into a thin disk is subjected to a rough polishing step or a finishing polishing step in which the surface of the silicon wafer is mirror- , And more preferably the finish polishing step.

[31] When the water-soluble polymer contained in the rinsing composition according to any one of [1] to [26] is referred to as water-soluble polymer A,

A polishing step of polishing a silicon wafer to be polished using a polishing liquid composition comprising silica particles, a water-soluble polymer B and a nitrogen-basic compound and an aqueous medium;

A rinsing step of rinsing the polished silicon wafer with the rinsing composition according to any one of [1] to [26]

And a cleaning step of cleaning the rinsed silicon wafer.

The water-soluble polymer (B)

A water-soluble polymer comprising the water-soluble polymer, silica particles, water and, if necessary, hydrochloric acid or ammonia, the concentration of the water-soluble polymer being 0.01 mass%, the concentration of the silica particles being 0.1 mass%, and the pH at 25 ° C being 10.0 Containing silica aqueous dispersion (water dispersion s), silica particles, water and, if necessary, hydrochloric acid or ammonia, wherein the concentration of the silica particles is 0.1% by mass and the pH at 25 캜 is 10.0 The method for producing a silicon wafer according to the above item [31], wherein the difference (z - z ₀ ) between the zeta potentials z ₀ of the water dispersion (water dispersion s ₀ ) is 15 수용 or more.

The water-soluble polymer (B)

Of the secondary particle diameter of the silica particles in the aqueous dispersion s D, the dispersion s ₀ ratio (D / D ₀₎ of the secondary particle diameter D ₀ of the silica particles in the water-soluble polymer is at least 1.10, wherein [32] And a silicon wafer.

The water-soluble polymer B is at least one selected from the group consisting of a polysaccharide, an alkyl acrylamide polymer, a polyvinyl alcohol, and a polyvinyl alcohol derivative (except an anion-modified polyvinyl alcohol) The method for producing a silicon wafer according to any one of [31] to [33] above.

The water-soluble polymer B is hydroxyethyl cellulose,

The method for producing a silicon wafer according to any one of [31] to [34], wherein the water-soluble polymer A is a polyglycerin derivative.

[36] The method for producing a silicon wafer according to any one of [31] to [35], wherein in the rinsing step, water rinsing treatment using water as a rinsing liquid is performed before the rinsing treatment.

[37] The method for producing a silicon wafer according to any one of [31] to [36], wherein the rinsing treatment in the rinsing step is carried out using a polishing apparatus used in the polishing step.

[38] A method for manufacturing a semiconductor substrate, comprising the step of manufacturing a silicon wafer by the method for manufacturing a silicon wafer according to any one of [31] to [37].

Example

1. How to measure various parameters

(1) Method of measuring zeta potential of aqueous dispersion S ₀ , S, s ₀ , s

The aqueous dispersion was placed in a capillary cell DTS1070, and the zeta potential was measured under the following conditions using "Zetasizer Nano ZS" manufactured by Malvern Corporation.

Sample: Refractive index: 1.450 Absorption rate: 0.010

Dispersion: viscosity: 0.8872 cP, refractive index: 1.330, dielectric constant: 78.5

Temperature: 25 ℃

(1-1) Preparation of silica water dispersion (aqueous dispersion S ₀ )

Ion exchanged water was added to a silica particle stock solution ("PL-3" manufactured by Fuso Chemical Co., Ltd.), and then an aqueous hydrochloric acid solution or an aqueous ammonia solution was added thereto so that the pH at 25 ° C was 7.0, 0.1% by mass of water dispersion S ₀ was obtained.

(1-2) Preparation of water-soluble polymer-containing silica water dispersion (aqueous dispersion S)

To each ion-exchanged water, each water-soluble polymer A and then a silica particle stock solution (" PL-3 " Thereafter, an aqueous hydrochloric acid solution or an aqueous ammonia solution was added thereto to obtain an aqueous dispersion S having a concentration of the water-soluble polymer of 0.1% by mass and a concentration of the silica particles of 0.1% by mass so that the pH at 25 캜 was 7.0.

(2-1) Preparation of silica water dispersion (aqueous dispersion s ₀ )

Ion-exchanged water was added to a silica particle stock solution ("PL-3" manufactured by Fuso Chemical Co., Ltd.), and then an aqueous hydrochloric acid solution or an aqueous ammonia solution was added thereto to adjust the pH at 25 ° C to 10.0, 0.1% by mass of water dispersion s ₀ was obtained.

(2-2) Preparation of water-soluble polymer-containing silica water dispersion (aqueous dispersion liquid s)

To each ion-exchanged water, each of the water-soluble polymer B and a silica particle stock solution (" PL-3 " Thereafter, an aqueous hydrochloric acid solution or an aqueous ammonia solution was added to this to obtain a pH of 10.0 at 25 ° C to obtain an aqueous dispersion s having a concentration of the water-soluble polymer of 0.01% by mass and a concentration of the silica particles of 0.1% by mass.

(2) Method for measuring secondary particle size of silica particles

The silica water dispersion S ₀ , S, s ₀ , s was placed in a Disposable Sizing Cuvette (polystyrene 10 mm cell) up to a height of 10 mm from the bottom of the bottom, and then subjected to dynamic light scattering method using "Zetasizer Nano ZS" , And the value of the Z average particle diameter was defined as the secondary particle diameter d ₀ , d, D ₀ , D of the silica water dispersion S ₀ , S, s ₀ , s. Measurement conditions are described below.

Sample: Refractive index: 1.450, Absorption rate: 0.010

Dispersion: viscosity: 0.8872 cP, refractive index: 1.330

Temperature: 25 ℃

(3) Measurement of weight average molecular weight of water-soluble polymer

The weight average molecular weight of the water-soluble polymer A used in the preparation of the rinse composition and the water-soluble polymer B used in the preparation of the polishing liquid composition was determined based on the peak in the chromatogram obtained by gel permeation chromatography (GPC) Respectively.

Device: HLC-8320 GPC (Tosoh Corporation, integrated detector)

Column: GMPWXL + GMPWXL (Anion)

Eluent: 0.2 M phosphoric acid buffer / CH ₃ CN = 9/1

Flow rate: 0.5 ml / min

Column temperature: 40 DEG C

Detector: RI detector

Standard material: Monodisperse polyethylene glycol whose weight average molecular weight is already known

2. Preparation of rinse composition

The water-soluble polymer A and ion-exchanged water described in Tables 1 and 2 were stirred and mixed, and if necessary, the pH value at 25 ° C was measured using an aqueous hydrochloric acid solution or 28 mass% ammonia water (Kishida Chemical Co., Was adjusted to 7.0 to obtain rinse compositions (all concentrates) of Examples 1 to 17 and Comparative Examples 1 to 5. However, in Example 9, the pH was adjusted to 4.0, in Example 10, the pH was adjusted to 10.0, and in Comparative Example 5, the ammonia concentration was adjusted to 5 ppm. The remainder excluding the water-soluble polymer, hydrochloric acid or ammonia is ion-exchanged water. The content of each component in Table 1 is a value for the rinse composition obtained by diluting the concentrated liquid to 20 times. The rinse compositions (all concentrates) of Examples 18 to 27 and Comparative Example 6 were adjusted so that the content of the water-soluble polymer A was 0.05% by mass when the pH at 25 ° C was 7.0 and diluted 20-fold. However, in Examples 25 to 27, 0.049% by mass of polyglycerol alkyl ether and 0.001% by mass of water soluble polymer having a betaine structure were prepared.

Details of the water-soluble polymers used in preparing the rinse compositions of Examples 1 to 27 and Comparative Examples 1 to 6, and the abrasive compositions of Examples 18 to 27 and Comparative Examples 6 are as follows.

A1: PGL 20PW (polyglycerin 20-mer): manufactured by Daicel

A2: PGL XPW (polyglycerin 40-dimers) manufactured by Daicel Chemical Industries, Ltd.

A3: PGL 100PW (polyglycerin polymer): manufactured by Daicel Chemical Industries, Ltd.

A4: Celmoris B044 (polyglycerin 20-mer lauryl ether) manufactured by Daicel Chemical Industries, Ltd.

A5: Polyacrylamide (Mw 10,000): manufactured by Polysciences

A6: Polyacrylamide (Mw 600,000 ~ 1,000,000): manufactured by Polysciences

A7: Kose line L-3266 (Mw 23,000) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.

A8: Colicot IR (Mw 26,500): manufactured by BASF

A9: Lipidure-HM (Mw 100,000): Nichi-like manufacture

A10: Lipidure-PMB (Mw 600,000, molar ratio (MPC / BMA) = 80:20)

A11: MPC / LMA (Mw 100,000): manufactured by Kao Corporation

A51: Poly (N-isopropylacrylamide) (Mn 20,000 ~ 40,000) manufactured by ALDRICH

A52: SE400 (Mw 250000): manufactured by Daicel

A53: PVA-117 (Mw 75000): manufactured by Kuraray Co.

A54: Poly (ethyleneoxide) (Mw 200000): manufactured by Polysciences

A55: n-Decylpentaoxyethylene: manufactured by Bachem AG

A56: polyhydroxyethyl acrylamide (Mw 700000)

Details of each constituent unit of the water-soluble polymers A9 to A11 are shown in Table 3 below, and the method of synthesizing the water-soluble polymer A11 is as follows.

[Water-soluble polymer A11]

10.0 g of ethanol was placed in a four-necked flask having an inner volume of 300 ml, and the temperature was raised to 70 캜. Thereafter, a solution obtained by mixing 5.0 g of MPC (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.1 g of LMA (manufactured by Wako Pure Chemical Industries, Ltd.) and 10.0 g of ethanol and a solution obtained by dissolving 2,2'-azobis Nitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) (0.021 g) and ethanol (4.4 g) were separately added dropwise over 2 hours to polymerize. After aging for 6 hours, the solvent was distilled off under reduced pressure and replaced with water to obtain a polymer aqueous solution containing water-soluble polymer A11 (a copolymer of MPC and LMA). The molar ratio (MPC / LMA) of the constituent units in the water-soluble polymer A11 was 80/20, and the weight average molecular weight of the water-soluble polymer A11 was 100,000.

3. Rinse method

The rinsing composition obtained by diluting the rinse composition (concentrated liquid) 20 times with ion-exchanged water was subjected to filtration with a filter (Compact Cartridge Filter "MCP-LX-C10S" manufactured by Advanetek Co., Ltd.) immediately before the rinse treatment was started, The following silicon wafer (silicon single-sided mirror surface wafer having a diameter of 200 mm (conduction type: P, crystal orientation: 100, resistivity: 0.1 Ω · cm or more and less than 100 Ω · cm) was rinsed under the following rinsing conditions. Prior to the rinsing treatment, the abrasive composition commercially available on the silicon wafer was preliminarily baked. The haze of the silicon wafer, which was supplied to the finish polishing after completion of the blanking, was 2.680 (ppm). Haze is a value at the dark-background wide oblique incident channel (DWO) measured using "Surfscan SP1-DLS" manufactured by KLA Tencor. Thereafter, finish polishing was carried out under the following conditions, and immediately thereafter, each rinse composition was rinsed under the following conditions.

[Abrasive composition used for finish polishing]

The abrasive composition used in the finish polishing carried out before the rinsing step using the rinse compositions of Examples 1 to 17 and Comparative Examples 1 to 5 was SE-400 (HEC manufactured by Daicel Co., Ltd., molecular weight: 250,000) , Ion exchanged water were mixed with stirring, and the mixture was stirred at room temperature for 1 hour to prepare a solution. The mixture was stirred at room temperature for 1 hour, The concentrate was obtained, and then the concentrate was diluted 40 times with ion-exchanged water just before use. The composition of the abrasive composition used in the finish polishing is as follows.

Silica particles (PL-3, average primary particle diameter 35 nm, average secondary particle diameter 69 nm, association degree 2.0): 0.17 mass%

HEC (SE-400): 0.01 mass%

Ammonia: 0.01 mass%

PEG (weight average molecular weight 6000); 0.0008 mass%

The compositions of the polishing liquid compositions of Examples 18 to 27 and Comparative Example 6 shown in Table 2 are as follows.

Silica particles (PL-3, average primary particle diameter 35 nm, average secondary particle diameter 69 nm, association degree 2.0): 0.17 mass%

Water-soluble polymer B: 0.01 mass%

Ammonia: 0.01 mass%

PEG (weight average molecular weight 6000); 0.0008 mass%

[Finishing Polishing Conditions]

Grinding machine: GRIND-X SPP600s 8-inch grinding machine manufactured by Okamoto

Polishing pad: suede pad manufactured by Toorekotex Co. (Asuka hardness: 64, thickness: 1.37 mm, snap length: 450 탆, aperture: 60 탆)

Silicon wafer polishing pressure: 100 g / cm < 2 >

Spinning speed: 60 rpm

Polishing time: 5 minutes

Feed rate of abrasive composition: 150 g / min

The temperature of the abrasive composition: 23 DEG C

Carrier rotation speed: 60 rpm

[Rinse condition]

Grinding machine: GRIND-X SPP600s 8-inch grinding machine manufactured by Okamoto

Polishing pad: Suede pad manufactured by Toorekotex Co. (Asuka hardness: 64, thickness: 1.37 mm, nap length: 450 um, aperture: 60 um)

Silicon wafer Rinse pressure: 60 g / cm < 2 >

Spinning speed: 30 rpm

Rinse time: 10 seconds

Feed rate of the rinse composition: 1000 ml / min

Temperature of the rinse composition: 23 DEG C

Carrier rotation speed: 30 rpm

4. Cleaning method

After the rinsing process, the silicon wafer was subjected to ozone cleaning and diphosphoric acid cleaning. In ozone cleaning, an aqueous solution containing 20 ppm of ozone was jetted from the nozzle toward the center of a silicon wafer rotated at 600 rpm at a flow rate of 1 l / min for 3 minutes. At this time, the temperature of the ozonated water was set at room temperature. Next, the hydrofluoric acid was washed. In the dilute hydrofluoric acid cleaning, an aqueous solution containing 0.5% by mass of ammonium hydrogen fluoride (special grade: Nacalai Tesque Co., Ltd.) was injected from the nozzle for 5 seconds toward the center of a silicon wafer rotating at 600 rpm at a flow rate of 1 l / min. A total of two sets of the ozone cleaning and dilute hydrofluoric acid cleaning were performed, and finally, spin drying was performed. In spin drying, the silicon wafer was rotated at 1500 rpm.

5. Evaluation of LPD on Silicon Wafer

The LPD on the surface of the silicon wafer after cleaning was evaluated by measuring the number of particles having a particle diameter of 45 nm or more on the surface of the silicon wafer using a surface roughness measuring apparatus "Surfscan SP1-DLS" (manufactured by KLA Tencor Corporation). The evaluation results of the LPD indicate that the smaller the value, the fewer the surface defects. The LPD measurement was carried out for each of two silicon wafers, and the average values thereof are shown in Tables 1 and 2.

6. Evaluation of polishing rate

The polishing rate was evaluated by the following method. The weight of each silicon wafer before and after polishing was measured using a precision balance ("BP-210S" manufactured by Sartorius Co.), and the obtained weight difference was divided by the density, area and polishing time of the silicon wafer, Respectively. The results are shown in Table 2, which is a relative value obtained by setting the polishing rate of Comparative Example 6 at 1.00.

As shown in Table 1, by using the rinse compositions of Examples 1 to 17, it was possible to satisfactorily reduce the LPD as compared with the rinse compositions of Comparative Examples 1 to 5. Therefore, by using the rinse compositions of Examples 1 to 17, it is possible to shorten the cleaning time as compared with the rinse compositions of Comparative Examples 1 to 5.

As shown in Table 2, in Examples 18 to 27 in which the water-soluble polymer A in which the potential difference (Z - Z ₀ ) was 25 ㎷ or less was used, in comparison with Comparative Example 6, the polishing rate and the LPD Both can be compatible.

Industrial availability

Use of the rinse composition of the present invention can shorten the cleaning time of the silicon wafer, and thus contributes to improvement in productivity and cost reduction in the production of semiconductor substrates.

Claims (16)

A rinse composition for a silicon wafer comprising a water-soluble polymer and an aqueous medium,
The water-
Wherein the concentration of the water-soluble polymer is 0.1% by mass, the concentration of the silica particles is 0.1% by mass, the pH at 25 ° C is 7.0, and the water-soluble polymer A zeta potential Z of a polymer-containing silica water dispersion (aqueous dispersion S), silica particles, water and, if necessary, hydrochloric acid or ammonia, wherein the concentration of the silica particles is 0.1% by mass and the pH at 25 캜 is 7.0 a silica aqueous dispersion (aqueous dispersion S ₀₎ the zeta potential Z ₀ of the difference (Z - Z ₀₎ is, the water-soluble polymer is not more than 25 ㎷, rinsing agent composition for a silicon wafer. A rinse composition for a silicon wafer comprising a water-soluble polymer and an aqueous medium,
Wherein the water-soluble polymer is at least one selected from the group consisting of polyglycerin, polyglycerin derivatives, polyglycidol, polyglycidol derivatives, polyvinyl alcohol derivatives, and polyacrylamides. Composition. The method according to claim 1,
The water-
And a secondary particle diameter of the silica particles in aqueous dispersion S wherein d, for the dispersion S ₀ ratio of the secondary particle diameter of the silica particles d ₀ (d / d ₀₎ is, the water-soluble polymer is not more than 1.35, the silicon wafer rinsed / RTI > The method according to claim 1 or 3,
Wherein the water-soluble polymer is at least one selected from the group consisting of polyglycerin, polyglycerin derivatives, polyglycidol, polyglycidol derivatives, polyvinyl alcohol derivatives, and polyacrylamides. 5. The method of claim 4,
Wherein the polyglycerin derivative is an alkyl ether of polyglycerin. 6. The method according to any one of claims 1 to 5,
A rinse composition for a silicon wafer, further comprising a basic compound. A rinsing method of a silicon wafer comprising a step of rinsing a polished silicon wafer with the rinsing composition according to any one of claims 1 to 6. And rinsing the polished silicon wafer with the rinsing composition according to any one of claims 1 to 6. When the water-soluble polymer contained in the rinsing composition according to any one of claims 1 to 6 is referred to as water-soluble polymer A,
A polishing step of polishing a silicon wafer to be polished using a polishing liquid composition comprising silica particles, a water-soluble polymer B and a nitrogen-basic compound and an aqueous medium;
A rinsing step of rinsing the polished silicon wafer with the rinsing composition according to any one of claims 1 to 6,
And a cleaning step of cleaning the rinsed silicon wafer. 10. The method of claim 9,
The water-soluble polymer (B)
Wherein the water-soluble polymer has a concentration of 0.01 mass%, a concentration of the silica particles of 0.1 mass%, and a pH at 25 캜 of 10.0, the water-soluble polymer being composed of the water-soluble polymer, silica particles, water and optionally hydrochloric acid or ammonia, A zeta potential z of a polymer-containing silica water dispersion (water dispersion s), silica particles, water and, if necessary, hydrochloric acid or ammonia, wherein the concentration of the silica particles is 0.1% by mass and the pH at 25 캜 is 10.0 Wherein the difference (z - z ₀ ) between the zeta potentials z ₀ of the phosphorus silicate aqueous dispersion (aqueous dispersion s ₀ ) is not less than 15 수용. 11. The method of claim 10,
The water-soluble polymer (B)
Preparation of the secondary particle diameter of the secondary particle diameter D and the silica particles in the aqueous dispersion s ₀ of the silica particles in the aqueous dispersion s D ₀ ratio (D / D ₀₎ a water-soluble polymer of a silicon wafer that is at least 1.10 of Way. 12. The method according to any one of claims 9 to 11,
Wherein the water-soluble polymer B is at least one selected from the group consisting of a polysaccharide, an alkyl acrylamide polymer, a polyvinyl alcohol, and a polyvinyl alcohol derivative (except an anion-modified polyvinyl alcohol) Gt; 13. The method according to any one of claims 9 to 12,
Wherein the water-soluble polymer B is hydroxyethyl cellulose,
Wherein the water-soluble polymer A is a polyglycerin derivative. 14. The method according to any one of claims 9 to 13,
In the rinsing step, a water rinsing treatment using water as a rinsing liquid is performed before the rinsing treatment. 15. The method according to any one of claims 9 to 14,
Wherein the rinsing treatment in the rinsing step is carried out using a polishing apparatus used in the polishing step. A manufacturing method of a semiconductor wafer comprising the step of manufacturing a silicon wafer by the manufacturing method of the silicon wafer according to any one of claims 9 to 15.