Post chemical mechanical polishing cleaning composition, post chemical mechanical polishing cleaning processing method and method for manufacturing semiconductor substrate

Abstract

To provide means to further reduce the number of residues remaining on the surface of polished abrasive objects after CMP.SOLUTION: A post chemical mechanical polishing cleaning composition contains the following (A) and (B) components and has a pH greater than 7.0 and less than 10.0, (A) component: nonionic polymer and (B) component: at least one compound selected from the group consisting of a compound having an amino group and a hydroxyl group, a compound of the formula (1): H2 N[(CH2)xNR1]yR2, and hexamethylenetetetramine.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a post-chemical mechanical abrasive cleaning composition, a post-chemical mechanical abrasive cleaning treatment method, and a method for manufacturing a semiconductor substrate. [Background technology]

[0002] In recent years, with the trend toward multilayer wiring on the surface of semiconductor substrates, a so-called chemical mechanical polishing (CMP) technique is used to physically polish and flatten the semiconductor substrate when manufacturing devices. CMP is a method for flattening the surface of an object to be polished (piece to be polished) such as a semiconductor substrate by using a polishing composition (slurry) containing abrasive grains such as silica, alumina, ceria, etc., an anticorrosive agent, a surfactant, etc., and the object to be polished (piece to be polished) is a wiring, plug, etc. made of silicon, polysilicon, silicon oxide, silicon nitride, metal, etc.

[0003] A large amount of impurities (also called foreign matter or residue) remain on the surface of a semiconductor substrate after the CMP process. The impurities include organic matter such as abrasive grains, metals, anticorrosives, and surfactants derived from the polishing composition used in CMP, silicon-containing materials that are the objects to be polished, silicon-containing materials and metals generated by polishing metal wiring, plugs, etc., and further organic matter such as pad waste generated from various pads, etc.

[0004] If the semiconductor substrate surface is contaminated by these impurities, it may adversely affect the electrical characteristics of the semiconductor and reduce the reliability of the device. Therefore, it is desirable to introduce a cleaning step after the CMP step to remove these impurities from the semiconductor substrate surface.

[0005] As such a cleaning composition, for example, Patent Document 1 discloses a polishing composition containing an organic compound containing specific atoms and having a molecular weight of 100 or more, a pH adjuster, and 0 to 1 mass % of abrasive grains. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2015-189899 A Summary of the Invention [Problem to be solved by the invention]

[0007] The polishing composition disclosed in Patent Document 1 can sufficiently remove impurities remaining on the surface of an object to be polished after CMP. However, as the quality required for semiconductor substrates has been increasing, there is a demand for a technology that can more efficiently and sufficiently remove foreign matter (residues) from the surface of semiconductor substrates.

[0008] Therefore, the present invention has been made in consideration of the above circumstances, and has an object to provide a means for further reducing the number of residues remaining on the surface of an object to be polished after CMP. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved by an alkaline post-chemical mechanical polishing cleaning composition containing a specific amino group-containing compound and a nonionic polymer, thereby completing the present invention.

[0010] That is, the above object is achieved by a post-chemical mechanical polishing cleaning composition comprising the following components (A) and (B) and having a pH of more than 7.0 and not more than 10.0: Component (A): Nonionic polymer Component (B): at least one compound selected from the group consisting of a compound having an amino group and a hydroxyl group, a compound represented by the following formula (1), and hexamethylenetetramine: Formula (1): H2N[(CH2) x NR 1 ] y R 2 In the above formula (1), R 1are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; each x is independently an integer of 1 to 10; and y is an integer of 1 to 8. Effect of the Invention

[0011] According to the present invention, the number of residues remaining on the surface of the object polished after CMP can be further reduced. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention provides a post-chemical mechanical polishing cleaning composition comprising the following components (A) and (B) and having a pH greater than 7.0 and not greater than 10.0: Component (A): Nonionic polymer Component (B): at least one compound selected from the group consisting of a compound having an amino group and a hydroxyl group, a compound represented by the following formula (1), and hexamethylenetetramine: Formula (1): H2N[(CH2) x NR 1 ] y R 2 In the above formula (1), R 1 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; each x is independently an integer of 1 to 10; and y is an integer of 1 to 8.

[0013] In this specification, the post-chemical mechanical polishing cleaning composition having the above-mentioned configuration is also referred to as "the post-chemical mechanical polishing cleaning composition of the present invention," "the post-CMP cleaning composition" or "the post-CMP cleaning composition of the present invention."

[0014] Such a post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) of the present invention can more efficiently and thoroughly remove residues (e.g., abrasive residues, particularly silicon compounds, organic residues) remaining on the surface of a polished object (particularly a polished substrate having silicon-silicon bonds).

[0015] The present inventors speculate that the mechanism by which such a configuration can remove residues on the surface of a polished object is as follows.

[0016] The post-chemical mechanical polishing cleaning composition according to the present invention contains specific components (A) and (B). Of these, component (A) is adsorbed to the surface of the polished object by hydrophobic interaction and acts like a protective film. In addition, component (A) improves the wettability of the surface of the polished object, making it easier to form a water molecule film on the surface. As a result, the post-chemical mechanical polishing cleaning composition according to the present invention, by containing component (A), can not only suppress the adhesion of hydrophobic organic residues to the surface of the polished object, but also prevent the re-adhesion of organic residues. Therefore, the post-CMP cleaning composition according to the present invention can efficiently remove residues.

[0017] Component (B) is a compound having an amino group and a hydroxyl group, represented by the formula (1): H2N[(CH2) x NR 1 ] y R 2 and hexamethylenetetramine. That is, component (B) has a total of two or more amino groups (primary amino groups, secondary amino groups, and tertiary amino groups) and hydroxyl groups (-OH) (hereinafter collectively referred to as "interactive groups"). The amino groups (particularly the lone electron pair or cation present on the nitrogen atom of the amino group) and hydroxyl groups (particularly the positively (δ+)-polarized or negatively (δ-)-polarized hydroxyl groups (-OH)) are preferably at least one of the above-mentioned compounds. - H +Under alkaline conditions, the (A) component (especially the positively (δ+) and negatively (δ-) polarized groups present in the (A) component (e.g., hydroxyl groups (-O - H + ) or carbonyl group (-C + (=O - ))) (for example, an amino group and a group in the (A) component form a hydrogen bond). These interactive groups interact with two (A) components to link these (A) components or bond (bridge) with two different points of one (A) component, forming a thicker protective film of the (A) component on the surface of the polished object. In addition, since the (B) component has a nitrogen atom, it is considered to be relatively easy to adsorb to the surface of the polished object (particularly, a polished substrate having a negative charge and a silicon-silicon bond) due to electrostatic attraction (hydrophobic attraction). Therefore, the (A) component is firmly adsorbed on the surface of the polished object via the (B) component. At the same time, the (B) component adsorbed on the surface of the polished object performs a nucleophilic attack on each atom constituting the polished object, stretching the bonds (particularly, silicon-silicon bonds) formed by the atoms, making them easier to break. As a result, etching of the polished surface of the object is accelerated, and it is assumed that the surface of the object is peeled off by the etching, and at the same time the residue is removed (residue can be reduced). In particular, when component (B) has a primary amino group (-NH2), the cation of the primary amino group (-NH3 + ) bonds with the anions of the polished object (particularly amorphous silicon) through electrostatic attraction, and the other interactive group interacts with component (A), allowing component (A) to bond thicker and more firmly with the polished object, thereby enabling residues to be removed more efficiently.

[0018] It should be noted that the above mechanism is based on speculation, and the present invention is not limited to the above mechanism in any way.

[0019] In the present specification, the amino group is not particularly limited, and includes a primary amino group (-NH2), a secondary amino group (-NHR; R is an alkyl group having 1 to 30 carbon atoms (preferably 1 to 20, more preferably 1 to 10) or an aryl group having 6 to 30 carbon atoms (preferably 6 to 20)), and a tertiary amino group (-NR2; R are each independently an alkyl group having 1 to 30 carbon atoms (preferably 1 to 20, more preferably 1 to 10) or an aryl group having 6 to 30 carbon atoms (preferably 6 to 20)). The amino group may also be a combination of the above primary to tertiary amino groups. Furthermore, when multiple (two or more) amino groups are present, these amino groups may be linked together to form -NR'-NR"- (wherein R' and R" are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms (preferably 1 to 20, more preferably 1 to 10), or an aryl group having 6 to 30 carbon atoms (preferably 6 to 20). However, the amino group may be a quaternary ammonium salt (-NR4 + X - ) is not included.

[0020] In this specification, the hydroxyl group refers to -OH itself, and does not include groups having an -OH group (for example, a carboxyl group).

[0021] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be modified in various ways within the scope of the claims. In addition, the embodiments described in this specification can be combined in any way to form other embodiments. In this specification, unless otherwise specified, operations and measurements of physical properties are performed under conditions of room temperature (20°C to 25°C) and relative humidity of 40% RH to 50% RH. In addition, "X and / or Y" means that X and Y are each included, and the combination thereof.

[0022] [Residue] In this specification, residue refers to foreign matter attached to the surface of the polished object. Examples of residue are not particularly limited, but include, for example, residue derived from the object to be polished, organic residue described later, particle residue derived from the abrasive grain contained in the polishing composition (abrasive grain residue), residue composed of components other than particle residue and organic residue, mixture of particle residue and organic residue, and other residues.

[0023] The total number of residues refers to the total number of all residues regardless of type. The total number of residues can be measured using a wafer defect inspection device. The number of residues refers to the total number of specific residues. Details of the method for measuring the number of residues will be described in the examples below.

[0024] In this specification, organic residue refers to components of foreign matter adhering to the surface of a polished object (object to be surface-treated) that are composed of organic substances such as organic low molecular weight compounds and high molecular weight compounds, organic salts, etc.

[0025] Examples of organic residues adhering to the polished object include pad waste generated from the pad used in the polishing step or rinse polishing step described below, or components derived from additives contained in the polishing composition used in the polishing step or the post-CMP cleaning composition used in the rinse polishing step.

[0026] Since organic residues and other foreign matter are significantly different in color and shape, whether or not a foreign matter is an organic residue can be determined by visual inspection using an SEM. In addition, whether or not a foreign matter is an organic residue can be determined by elemental analysis using an energy dispersive X-ray analyzer (EDX) as necessary. The number of organic residues can be measured using a wafer defect inspection device and SEM or EDX elemental analysis.

[0027] The abrasive grain residues attached to the polished object are particle residues derived from the abrasive grains contained in the polishing composition. Here, examples of the abrasive grains include particles made of metal oxides such as silicon compounds such as silica (silicon oxide), aluminum compounds such as alumina, zirconium compounds such as zirconia, and titanium compounds such as titania. The abrasive grain residues may be derived from the above-mentioned single abrasive grain or a mixture of two or more abrasive grains. Among these, when the abrasive grain residues are residues derived from silicon compounds such as silica (particularly colloidal silica), the effect of the present invention can be particularly remarkable. Therefore, in one embodiment of the present invention, the post-chemical mechanical polishing cleaning composition is a post-chemical mechanical polishing cleaning composition for removing silicon compounds. In one embodiment of the present invention, the post-chemical mechanical polishing cleaning composition is a post-chemical mechanical polishing cleaning composition for removing silica abrasive grain residues. In one embodiment of the present invention, the post-chemical mechanical polishing cleaning composition is a post-chemical mechanical polishing cleaning composition for removing colloidal silica abrasive grain residues.

[0028] [Polished object] In this specification, the term "polished object" refers to an object that has been polished in a polishing process, such as a chemical mechanical polishing (CMP) process.

[0029] The material contained in the ground object according to the present invention is not particularly limited, but from the viewpoint that sufficient etching is promoted by the adsorption of the (A) component and the effect of the present invention is easily obtained, a Si-based material is preferable. Examples of the Si-based material include a material containing silicon-silicon bonds (silicon material), a material containing nitrogen-silicon bonds, and a material containing oxygen-silicon bonds. The ground object may be composed of a plurality of the above materials.

[0030] Among these, the material contained in the polished object is preferably a material containing silicon-silicon bonds (silicon material) because the effect of the post-CMP cleaning composition according to one embodiment of the present invention is more pronounced. That is, the post-CMP cleaning composition according to one embodiment of the present invention is preferably used in a post-chemical mechanical polishing cleaning treatment (surface treatment) of a substrate having a surface made of a material containing silicon-silicon bonds (silicon material).

[0031] Here, examples of materials containing silicon-silicon bonds include polysilicon (polycrystalline silicon), amorphous silicon (non-crystalline silicon), and single crystal silicon. These materials may be doped with impurities. In this case, the impurities may be either n-type or p-type, and examples of p-type impurities include Group 13 elements such as boron (B), aluminum (Al), gallium (Ga), and indium (In), while examples of n-type impurities include Group 15 elements such as phosphorus (P), arsenic (As), bismuth (Bi), and antimony (Sb).

[0032] In one embodiment of the present invention, the material (silicon material) containing silicon-silicon bonds includes at least one material selected from the group consisting of polysilicon, amorphous silicon, and single crystal silicon. From the viewpoint of obtaining the effects of the present invention more significantly, the material (silicon material) containing silicon-silicon bonds is more preferably polysilicon, amorphous silicon, or single crystal silicon, even more preferably polysilicon or amorphous silicon, and particularly preferably amorphous silicon. That is, the post-chemical mechanical polishing cleaning composition according to one embodiment of the present invention is more preferably used in a post-chemical mechanical polishing cleaning process (post-CMP cleaning process, surface treatment) of a substrate (polished object) having a surface made of polysilicon, amorphous silicon, or single crystal silicon. The post-chemical mechanical polishing cleaning composition according to one embodiment of the present invention is more preferably used in a post-chemical mechanical polishing cleaning process of a substrate (polished object) having a surface made of polysilicon or amorphous silicon. The post-chemical mechanical polishing cleaning composition according to one embodiment of the present invention is particularly preferably used in a post-chemical mechanical polishing cleaning process of a substrate (polished object) having a surface made of amorphous silicon.

[0033] [Post-Chemical Mechanical Polishing Cleaning Compositions (Post-CMP Cleaning Compositions)] The post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) of the present invention is used to reduce residues on the surface of a polished object.

[0034] <Component (A)> The post chemical mechanical polishing cleaning composition according to the present invention contains a nonionic polymer as component (A). The term "nonionic polymer" used herein refers to a polymer that does not have an anionic group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group, or a cationic group such as a quaternary ammonium group, in the molecule.

[0035] The nonionic polymer acts as a protective film on the surface of the polished object. The nonionic polymer also improves the wettability of the surface of the polished object without interfering with the control of the zeta potential (positive charging) of the polished object, abrasive residue, organic residue, etc. by component (B). Therefore, the presence of component (A) can promote the removal of residues on the surface of the polished object (suppress the adhesion or re-adhesion of organic residue, etc.).

[0036] The nonionic polymer may be a polymer having the same (homopolymer) or different (copolymer) repeating units, and typically a compound having a weight average molecular weight (Mw) of 1,000 or more. When the nonionic polymer is a copolymer, the copolymer may be in the form of a block copolymer, a random copolymer, a graft copolymer, or an alternating copolymer.

[0037] Examples of nonionic polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, poly N-vinylacetamide, polyamines, polyvinyl ethers (polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl isobutyl ether, etc.), water-soluble polysaccharides such as polyglycerin, polyethylene glycol, polypropylene glycol, hydroxyethyl cellulose, alginic acid polyhydric alcohol ester, water-soluble urea resin, dextrin derivatives, casein, etc. In addition to those having such a main chain structure, graft copolymers having a nonionic polymer structure in the side chain can also be suitably used. Furthermore, copolymers such as ethylene-vinyl alcohol copolymer and butenediol-vinyl alcohol copolymer can also be used. These nonionic polymers can be used alone or in combination of two or more.

[0038] Among these, from the viewpoint of further improving the effect of removing residues, it is preferable that the nonionic polymer includes (1) a nonionic polymer containing a nitrogen atom and / or (2) a nonionic polymer containing a hydroxyl group.

[0039] Suitable examples of the nonionic polymer of (1) and / or (2) above include the following: polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, poly N-vinylacetamide, polyethylene glycol, hydroxyethyl cellulose, butenediol-vinyl alcohol copolymer, etc. Therefore, in one embodiment, the nonionic polymer as component (A) preferably includes at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, poly N-vinylacetamide, polyethylene glycol, hydroxyethyl cellulose, and butenediol-vinyl alcohol copolymer. In yet another embodiment, the nonionic polymer preferably includes at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, and poly N-vinylacetamide. In yet another embodiment, the nonionic polymer preferably includes polyvinyl alcohol or polyvinylpyrrolidone. In yet another embodiment, the nonionic polymer preferably includes polyvinyl alcohol. In yet another embodiment, the nonionic polymer is preferably polyvinyl alcohol. These nonionic polymers are easily adsorbed to the surface of polished objects (especially polished objects containing silicon-silicon bonds), and thus a water molecule film is easily formed. As a result, the adhesion and re-adhesion of organic residues is effectively suppressed, and the effect of removing residues is further improved.

[0040] The reason why the above nonionic polymers (1) and (2) are preferable as the nonionic polymer is considered as follows.

[0041] As in the above (1), when a nonionic polymer containing nitrogen atoms is used, the nitrogen atoms contained in the nonionic polymer and the hydroxyl groups (-OH) present on the surface of a substrate (polished object) having a surface made of a silicon material are likely to be polarized positively (δ+) and negatively (δ-), respectively, so that the nonionic polymer is likely to be adsorbed to the surface of the substrate (polished object) having a surface made of a silicon material. Therefore, it is considered that the water molecule film is easily formed as described above, and as a result, the adhesion and re-adhesion of organic residues can be effectively suppressed. Therefore, in one embodiment of the present invention, it is preferable that the nonionic polymer contains nitrogen atoms. In the above embodiment, it is preferable that the nonionic polymer contains at least one selected from the group consisting of polyvinylpyrrolidone, polyacrylamide, and poly-N-vinylacetamide. Furthermore, it is more preferable that the nonionic polymer contains polyvinylpyrrolidone and / or poly-N-vinylacetamide. Furthermore, it is even more preferable that the nonionic polymer contains polyvinylpyrrolidone. Furthermore, it is particularly preferable that the nonionic polymer is polyvinylpyrrolidone.

[0042] As in the above (2), when a nonionic polymer containing a hydroxyl group (-OH) is used, the nonionic polymer is relatively easily adsorbed to the surface of a substrate (polished object) having a surface made of a silicon material, and as a result, the formation of the water molecule film as described above is facilitated, and it is considered that the adhesion and re-adhesion of organic residues can be effectively suppressed. Here, the present inventors have found that in the above embodiment (2), when the component (B) according to the present invention is used in combination, the effect of reducing residues is particularly improved. That is, it is considered that two or more interactive groups (amino groups (primary amino groups, secondary amino groups, and tertiary amino groups) and hydroxyl groups (-OH)) present in the component (B) interact more easily with the hydroxyl groups (-OH) contained in the component (A) under alkaline conditions, and the hydroxyl groups of the component (A) are more efficiently and more firmly bound to the interactive groups of the component (B). As a result, a thicker protective film of the component (A) can be formed on the surface of the polished object. In addition, the component (B) adsorbed on the polished object also makes it easier for the component (A) to be adsorbed on the polished object. That is, the component (B) having two or more interactive groups makes it easier for the component (A) to form a thicker protective film (water molecule film) more firmly on the surface of the polished object. Therefore, it is considered that the wettability of the surface of the polished object is further improved, and the adhesion and re-adhesion of organic residues can be effectively suppressed. The above effect is particularly remarkable when the component (B) has two or more amino groups. Note that the above mechanism is based on speculation, and the present invention is not limited to the above mechanism.

[0043] Therefore, in one embodiment of the present invention, the nonionic polymer contains a hydroxyl group. In the above embodiment, the nonionic polymer preferably contains at least one selected from the group consisting of polyvinyl alcohol, polyethylene glycol, hydroxyethyl cellulose, and butenediol-vinyl alcohol copolymer. Furthermore, the nonionic polymer more preferably contains polyvinyl alcohol. Furthermore, the nonionic polymer is particularly preferably polyvinyl alcohol.

[0044] The lower limit of the weight average molecular weight (Mw) of the nonionic polymer is preferably 1,000 or more, more preferably 3,000 or more, even more preferably more than 5,000, particularly preferably 8,000 or more, and most preferably more than 9,000. The upper limit of the weight average molecular weight (Mw) of the nonionic polymer is preferably 1,000,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, particularly preferably 50,000 or less, and most preferably less than 50,000. As an example, the weight average molecular weight (Mw) of the nonionic polymer is preferably 1,000 or more and 1,000,000 or less, more preferably 3,000 or more and 100,000 or less, even more preferably more than 5,000 and 80,000 or less, particularly preferably 8,000 or more and 50,000 or less, and most preferably more than 9,000 and less than 50,000.

[0045] The weight average molecular weight (Mw) of the nonionic polymer can be measured as a polyethylene glycol equivalent value using gel permeation chromatography (GPC), and details of the measurement method will be described in the Examples below.

[0046] The nonionic polymer that can be used as component (A) may be produced by synthesis or may be a commercially available product. Examples of commercially available products include JMR (registered trademark)-10HH, JMR (registered trademark)-3HH (both from Nippon Vinyl Acetate & Poval Co., Ltd.), Pitzcol (registered trademark) K30A, K30L (both from Daiichi Kogyo Seiyaku Co., Ltd.), CMC Daicel (registered trademark) 1150, 1170 (both from Daicel Miraize Co., Ltd.), GE191-104, 107 (both from Showa Denko K.K.), etc.

[0047] The nonionic polymer as the component (A) may be used either individually or in combination of two or more.

[0048] The content of the (A) component in the post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) is appropriately set according to the type of the (A) component used and the desired effect. The content of the (A) component is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.03% by mass or more, based on the total mass of the post-CMP cleaning composition being 100% by mass (based on the post-CMP cleaning composition). The upper limit of the content of the (A) component in the post-CMP cleaning composition is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less, based on the total mass of the post-CMP cleaning composition being 100% by mass (based on the post-CMP cleaning composition). In one embodiment of the present invention, the content of the (A) component is 0.0001% by mass or more and 1.5% by mass or less, based on the total mass of the post-CMP cleaning composition being 100% by mass (based on the post-CMP cleaning composition). In one embodiment of the present invention, the content of component (A) is 0.001% by mass or more and 1.0% by mass or less (relative to the post-CMP cleaning composition), with the total mass of the post-CMP cleaning composition being 100% by mass. In one embodiment of the present invention, the content of component (A) is 0.01% by mass or more and 0.5% by mass or less (relative to the post-CMP cleaning composition), with the total mass of the post-CMP cleaning composition being 100% by mass. In one embodiment of the present invention, the content of component (A) is 0.03% by mass or more and 0.3% by mass or less (relative to the post-CMP cleaning composition), with the total mass of the post-CMP cleaning composition being 100% by mass. When the post-CMP cleaning composition contains two or more types of component (A), the content of component (A) refers to the total amount of these.

[0049] <(B) component> The post-chemical mechanical polishing cleaning composition according to the present invention comprises, as component (B), a compound having an amino group (a primary, secondary or tertiary amino group) and a hydroxyl group (-OH), represented by the formula (1): H2N[(CH2) x NR 1 ] y R 2and hexamethylenetetramine. Component (B) may contain atoms (other atoms) other than carbon, hydrogen, nitrogen, and oxygen atoms, but preferably does not contain other atoms (i.e., component (B) is composed only of carbon, hydrogen, nitrogen, and oxygen atoms, or is composed only of carbon, hydrogen, and nitrogen atoms).

[0050] The compound having an amino group and a hydroxyl group as the component (B) may be any compound having one or more amino groups (primary amino group, secondary amino group, or tertiary amino group) and one or more hydroxyl groups (including the salt form of the hydroxyl group).Specific examples include 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, diethanolamine, triethanolamine, 2-(2-aminoethylamino)ethanol, trishydroxymethylaminomethane, 2-(methylamino)ethanol, 2-(2-aminoethoxy)ethanol, 2-amino-2-methyl-1-propanol, 1-dimethylamino-2-propanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, and salts thereof. When the hydroxyl group is in the form of a salt, examples of the salt include alkali metal salts such as sodium salts and potassium salts, ammonium salts, carbonates, and acetates.

[0051] Among these, from the viewpoint of further improving the residue reduction effect, it is preferable that the oxygen atom exists only as a hydroxyl group. Also, from the viewpoint of further improving the residue reduction effect, a compound having 1 to 3 amino groups and 1 to 3 hydroxyl groups is preferable, a compound having 1 or 2 primary or secondary amino groups (the total of the primary amino groups and the secondary amino groups is 1 to 2) and 1 or 2 hydroxyl groups is more preferable, and a compound having 1 primary or secondary amino group and 1 hydroxyl group is particularly preferable.

[0052] That is, in one embodiment of the present invention, component (B) contains at least one compound selected from the group consisting of 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, diethanolamine, triethanolamine, 2-(2-aminoethylamino)ethanol, trishydroxymethylaminomethane, 2-(methylamino)ethanol, 2-(2-aminoethoxy)ethanol, 2-amino-2-methyl-1-propanol, 1-dimethylamino-2-propanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-ethyl-1,3-propanediol. In one embodiment of the present invention, component (B) comprises at least one compound selected from the group consisting of 2-aminoethanol, 3-amino-1-propanol, diethanolamine, 2-(2-aminoethylamino)ethanol, 2-(methylamino)ethanol, 2-(2-aminoethoxy)ethanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, and 2-amino-2-ethyl-1,3-propanediol. In one embodiment of the present invention, component (B) comprises at least one compound selected from the group consisting of 2-aminoethanol, 3-amino-1-propanol, 2-(2-aminoethylamino)ethanol, 2-(methylamino)ethanol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. In one embodiment of the present invention, the (B) component is at least one compound selected from the group consisting of 2-aminoethanol, 3-amino-1-propanol, 2-(2-aminoethylamino)ethanol, 2-(methylamino)ethanol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. In one embodiment of the present invention, the (B) component includes at least one compound selected from the group consisting of 3-amino-1-propanol and 2-(methylamino)ethanol. In one embodiment of the present invention, the (B) component is at least one compound selected from the group consisting of 3-amino-1-propanol and 2-(methylamino)ethanol.

[0053] (B) Component of formula (1): H2N[(CH2) x NR 1 ] y R 2 In the case where the compound represented by the formula (1) is included, 1 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Here, [(CH2) x NR 1 If there are two or more [(CH2) x NR 1 ] in R 1 may be the same or different. 1 The alkyl group having 1 to 10 carbon atoms as the radical may be linear, branched, or cyclic.

[0054] Specific examples of the straight-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.

[0055] Specific examples of branched alkyl groups include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an isohexyl group, a 1,3-dimethylbutyl group, a 1-isopropylpropyl group, a 1,2-dimethylbutyl group, a 1,4-dimethylpentyl group, a 3-ethylpentyl group, a 2-methyl-1-isopropylpropyl group, a 1-ethyl-3-methylbutyl group, a 2-ethylhexyl group, a 3-methyl-1-isopropylbutyl group, a 2-methyl-1-isopropyl group, a 1-tert-butyl-2-methylpropyl group, and an isodecyl group.

[0056] Specific examples of the cyclic (alicyclic) alkyl group include cycloalkyl groups having 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0057] Among them, R 1 The alkyl group as is preferably linear or branched, and more preferably linear.

[0058] With respect to the alkyl group, the upper limit of the carbon number is preferably 8 or less, more preferably 6 or less, even more preferably 5 or less, and particularly preferably 3 or less, from the viewpoint of reducing residues (particularly organic residues). On the other hand, the lower limit of the carbon number is preferably 2 or more. Therefore, as an example, R 1 and R 2 The number of carbon atoms in the alkyl group as the alkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 6 or less, even more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1 or 2.

[0059] From the viewpoint of further improving the residue reduction effect, 1 is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, even more preferably a hydrogen atom, a methyl group, or an ethyl group, even more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0060] In the above formula (1), R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 2 Examples of the alkyl group having 1 to 10 carbon atoms as R 1 is the same as:

[0061] From the viewpoint of further improving the residue reduction effect, 2 is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, even more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0062] In the above formula (1), x is an integer of 1 or more and 10 or less. [(CH2) x NR 1 If there are two or more [(CH2) x NR 1 In order to further improve the residue reduction effect, x is preferably an integer of 1 to 8, more preferably 1 to 5, even more preferably 1 to 3, particularly preferably 2 or 3, and most preferably 2.

[0063] In the above formula (1), y is an integer of 1 or more and 8 or less. From the viewpoint of further improving the residue reduction effect, y is preferably 1 or more and 7 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less.

[0064] The compound represented by the above formula (1) includes methylenediamine (in formula (1), R 1 ,R 2 =H, x=1, y=1), ethylenediamine (wherein R 1 ,R 2 =H, x=2, y=1), diethylenetriamine (in formula (1), R 1 ,R 2 =H, x=2, y=2), triethylenetetramine (in formula (1), R 1 ,R 2 =H, x=2, y=3), tetraethylenepentamine (in formula (1), R 1 ,R 2 =H, x=2, y=4), pentaethylenehexamine (in formula (1), R 1 ,R 2 =H, x=2, y=5), hexaethyleneheptamine (in formula (1), R 1 ,R 2 =H, x=2, y=6), heptaethyleneoctamine (in formula (1), R 1 ,R 2 = H, x = 2, y = 7), propylenediamine (= diaminopropane) (in formula (1), R 1 ,R 2=H, x=3, y=1), diaminobutane (in formula (1), R 1 ,R 2 = H, x = 4, y = 1), diaminopentane (in formula (1), R 1 ,R 2 =H, x=5, y=1), diaminohexane (in formula (1), R 1 ,R 2 = H, x = 6, y = 1), diaminoheptane (in formula (1), R 1 ,R 2 = H, x = 7, y = 1), diaminooctane (in formula (1), R 1 ,R 2 = H, x = 8, y = 1), diaminononane (in formula (1), R 1 ,R 2 = H, x = 9, y = 1), diaminodecane (in formula (1), R 1 ,R 2 =H, x=10, y=1), dipropylenetriamine (in formula (1), R 1 ,R 2 =H, x=3, y=2), tripropylenetetramine (in formula (1), R 1 ,R 2 =H, x=3, y=3), tetrapropylenepentamine (in formula (1), R 1 ,R 2 =H, x=3, y=4).

[0065] Component (B) is R 1 is a hydrogen atom (i.e., both ends are primary amino groups or a combination of primary and secondary amino groups), and 1 and R 2It is more preferable that the (B) component contains a compound of formula (1) in which both ends are hydrogen atoms (i.e., both ends are primary amino groups), and it is particularly preferable to combine the (B) component with a nonionic polymer ((A) component) having a hydroxyl group (-OH). The reason why this combination is preferable is considered to be as follows. The (B) component has a total of two or more primary amino groups and secondary amino groups. It is considered that the primary and secondary amino groups (particularly the primary amino groups) interact more easily with the hydroxyl groups (-OH) contained in the (A) component, making it easier for the hydroxyl groups of the (A) component to be adsorbed by the (B) component. As a result, two (A) components are more easily linked via the (B) component, or the (B) component more easily crosslinks two different points of one (A) component. In addition, the (B) component adsorbed on the polished object also makes the (A) component more easily adsorbed on the polished object. Therefore, the (A) component can form a thicker and stronger protective film (water molecule film) on the surface of the polished object. Therefore, it is considered that the wettability of the surface of the polished object is improved, and the adhesion and re-adhesion of organic residues can be effectively suppressed. Note that the above mechanism is based on speculation, and the present invention is not limited to the above mechanism.

[0066] In one embodiment of the present invention, component (B) includes at least one compound selected from the group consisting of 2-aminoethanol, 3-amino-1-propanol, diethanolamine, 2-(2-aminoethylamino)ethanol, 2-(methylamino)ethanol, 2-(2-aminoethoxy)ethanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, the compound represented by the above formula (1), and hexamethylenetetramine. In one embodiment of the present invention, component (B) includes at least one compound selected from the group consisting of 2-aminoethanol, 3-amino-1-propanol, 2-(2-aminoethylamino)ethanol, 2-(methylamino)ethanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, the compound represented by the above formula (1), and hexamethylenetetramine. In one embodiment of the present invention, the component (B) is at least one compound selected from the group consisting of 2-aminoethanol, 3-amino-1-propanol, 2-(2-aminoethylamino)ethanol, 2-(methylamino)ethanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, the compound represented by the above formula (1), and hexamethylenetetramine. In one embodiment of the present invention, the component (B) contains at least one compound selected from the group consisting of 3-amino-1-propanol, 2-(methylamino)ethanol, the compound represented by the above formula (1), and hexamethylenetetramine. In one embodiment of the present invention, the component (B) contains at least one compound selected from the group consisting of the compound represented by the above formula (1) and hexamethylenetetramine. In one embodiment of the present invention, the component (B) is at least one compound selected from the group consisting of R 1 is a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, and R 2 is a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, x is 1 or more and 5 or less, and y is 1 or more and 8 or less, and at least one compound selected from the group consisting of hexamethylenetetramine. 1 is a hydrogen atom or a methyl group, and R2 is a hydrogen atom or a methyl group, x is 1 or more and 3 or less, and y is 1 or more and 5 or less, and hexamethylenetetramine. 1 is a hydrogen atom, and R 2 is a hydrogen atom, x is 2, and y is 1 to 3. In one embodiment of the present invention, component (B) comprises at least one compound selected from the group consisting of compounds represented by the above formula (1), in which R 1 is a hydrogen atom, and R 2 is a hydrogen atom, x is 2, and y is 1 or more and 3 or less, and is at least one compound selected from the group consisting of compounds represented by the above formula (1).

[0067] The compound that can be used as component (B) may be a synthetic product or a commercially available product. The compound as component (B) may be used alone or in combination of two or more kinds.

[0068] The content of the (B) component in the post-CMP cleaning composition is appropriately set according to the type of the (B) component used and the desired effect. The content of the (B) component is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and particularly preferably 0.04% by mass or more, based on the total mass of the post-CMP cleaning composition being 100% by mass (based on the post-CMP cleaning composition). The upper limit of the content of the (B) component in the post-CMP cleaning composition is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and particularly preferably 0.15% by mass or less, based on the total mass of the post-CMP cleaning composition being 100% by mass (based on the post-CMP cleaning composition). By setting the upper limit at such a value, the (B) component itself is prevented from becoming a residue, and the residue can be efficiently removed. In one embodiment of the present invention, the content of the (B) component is 0.01% by mass or more and 0.3% by mass or less, based on the total mass of the post-CMP cleaning composition being 100% by mass (based on the post-CMP cleaning composition). In one embodiment of the present invention, the content of component (B) is 0.02% by mass or more and 0.2% by mass or less (relative to the post-CMP cleaning composition), with the total mass of the post-CMP cleaning composition being 100% by mass. In one embodiment of the present invention, the content of component (B) is 0.04% by mass or more and 0.15% by mass or less (relative to the post-CMP cleaning composition), with the total mass of the post-CMP cleaning composition being 100% by mass. When the post-CMP cleaning composition contains two or more types of component (B), the content of component (B) refers to the total amount of these.

[0069] Alternatively or in addition to the above, the concentration of the component (B) in the post-CMP cleaning composition may be appropriately set. In this case, the amount of interactive groups present in the post-CMP cleaning composition, and therefore the interaction with the component (A), can be appropriately adjusted, which is preferable. Specifically, the concentration of the component (B) in the post-CMP cleaning composition is preferably 1 mM or more, more preferably 3 mM or more, and particularly preferably more than 5 mM. The upper limit of the concentration of the component (B) in the post-CMP cleaning composition is preferably 20 mM or less, more preferably 15 mM or less, and particularly preferably 10 mM or less. By setting the upper limit at such a value, the component (B) itself is prevented from becoming a residue, and the residue can be efficiently removed. In one embodiment of the present invention, the concentration of the component (B) is 1 mM or more and 20 mM or less. In one embodiment of the present invention, the concentration of the component (B) is 3 mM or more and 15 mM or less. In one embodiment of the present invention, the concentration of the component (B) is more than 5 mM and 10 mM or less. When the post-CMP cleaning composition contains two or more types of component (B), the concentration of component (B) refers to the total amount of these.

[0070] Instead of or in addition to the above, the mixing ratio of component (B) to component (A) in the post-chemical mechanical polishing cleaning composition may be appropriately set according to the types of component (B) and component (A) used and the desired effects. The mixing ratio of component (B) to component (A) ((B) component / (A) component content ratio) (mass ratio) is preferably 0.3 or more, more preferably 0.4 or more, still more preferably 0.5 or more, and particularly preferably 0.6 or more. The mixing ratio of component (B) to component (A) ((B) component / (A) component content ratio) (mass ratio) is preferably 5 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably less than 2. In one embodiment of the present invention, the mixing ratio of component (B) to component (A) ((B) component / (A) component content ratio) (mass ratio) is 0.3 or more and 5 or less. In one embodiment of the present invention, the mixing ratio of component (B) to component (A) ((B) component / (A) component content ratio) (mass ratio) is 0.4 or more and 3 or less. In one embodiment of the present invention, the mixing ratio of component (B) to component (A) ((B) component / (A) component content ratio) (mass ratio) is 0.5 or more and 2 or less. In one embodiment of the present invention, the mixing ratio of component (B) to component (A) ((B) component / (A) component content ratio) (mass ratio) is 0.6 or more and less than 2.

[0071] <pH adjuster ((C) component)> The post-chemical mechanical polishing cleaning composition according to the present invention essentially contains the above components (A) and (B), but in addition to these, it is preferably further contains a pH adjuster. That is, in a preferred form of the present invention, the post-chemical mechanical polishing cleaning composition further contains component (C): (C) component: pH adjuster.

[0072] The pH adjuster is not particularly limited, and any known pH adjuster used in the field of post-chemical mechanical polishing cleaning compositions (post-CMP cleaning compositions) can be used, and any known acid, base, or salt thereof can be used. Examples of pH adjusters include carboxylic acids such as formic acid, acetic acid, glycolic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, lactic acid, malic acid, tartaric acid, citric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, cinnamic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, aconitic acid, amino acids, and anthranilic acid, and sulfonic acids (isethioic acid). , camphorsulfonic acid, etc.), organic phosphonic acids (hydroxyethylidene diphosphonic acid, diethylenetriaminepentamethylenephosphonic acid, etc.); inorganic acids such as nitric acid, carbonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, hypophosphorous acid, phosphorous acid, phosphonic acid, boric acid, hydrofluoric acid, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid, etc.; alkali metal hydroxides such as potassium hydroxide (KOH) and sodium hydroxide (NaOH); alkali metal carbonates such as potassium carbonate (K2CO3) and sodium carbonate (Na2CO3); hydroxides of Group 2 elements; ammonia (ammonium hydroxide); organic bases such as quaternary ammonium hydroxide compounds, etc. The pH adjuster may be a synthetic product or a commercially available product. In addition, these pH adjusters may be used alone or in combination of two or more.

[0073] Among these, when the basicity of component (B) is relatively low and the pH of the desired post-CMP cleaning composition is relatively low, potassium hydroxide, sodium hydroxide, sodium carbonate, and ammonia are preferred, potassium hydroxide, sodium hydroxide, and ammonia are more preferred, and ammonia is particularly preferred. That is, in a preferred embodiment of the present invention, the pH adjuster is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium carbonate, and ammonia. In a more preferred embodiment of the present invention, the pH adjuster is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, and ammonia. In a particularly preferred embodiment of the present invention, the pH adjuster is ammonia.

[0074] On the other hand, when the basicity of the (B) component is relatively high and the pH of the desired post-CMP cleaning composition is relatively high, acetic acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, formic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, malic acid, citric acid, glycolic acid, tartaric acid, lactic acid, and hydroxyethylidene diphosphonic acid are preferred, and acetic acid is more preferred. That is, in a preferred embodiment of the present invention, the pH adjuster is at least one selected from the group consisting of acetic acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, formic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, malic acid, citric acid, glycolic acid, tartaric acid, lactic acid, and hydroxyethylidene diphosphonic acid. In a more preferred embodiment of the present invention, the pH adjuster is acetic acid.

[0075] In one embodiment of the invention, the pH adjuster is ammonia or acetic acid.

[0076] The content of the pH adjuster in the post-CMP cleaning composition may be appropriately selected so as to give the post-CMP cleaning composition a desired pH value, as described in detail below.

[0077] <pH of Post-Chemical Mechanical Polishing Cleaning Composition> The pH of the post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) according to the present invention is more than 7.0 and not more than 10.0. If the pH of the post-CMP cleaning composition is 7.0 or less, the residue remaining on the surface of the polished object cannot be sufficiently removed. From the viewpoint of further improving the effects of the present invention (particularly, removing the residue), the pH of the post-CMP cleaning composition is preferably 7.1 or more, more preferably 7.2 or more. The pH of the post-CMP cleaning composition is 10.0 or less. If the pH of the post-CMP cleaning composition is more than 10.0, the residue remaining on the surface of the polished object cannot be sufficiently removed. From the viewpoint of further improving the effects of the present invention (particularly, removing the residue), the pH of the post-CMP cleaning composition is preferably less than 10.0, more preferably 9.9 or less, even more preferably 9.5 or less, even more preferably 8.5 or less, particularly preferably less than 8.0, and most preferably 7.5 or less. That is, in one embodiment of the present invention, the pH of the post-CMP cleaning composition is 7.1 or more and less than 10.0. In one embodiment of the present invention, the pH of the post-CMP cleaning composition is 7.1 or more and 9.9 or less. In one embodiment of the present invention, the pH of the post-CMP cleaning composition is 7.2 or more and 9.5 or less. In one embodiment of the present invention, the pH of the post-CMP cleaning composition is 7.2 or more and less than 8.5. In one embodiment of the present invention, the pH of the post-CMP cleaning composition is 7.2 or more and less than 8.0. In one embodiment of the present invention, the pH of the post-CMP cleaning composition is 7.2 or more and less than 7.5. The pH of the post-CMP cleaning composition is measured by the method described in the Examples.

[0078] <Solvent> The post-chemical mechanical polishing cleaning composition according to the present invention preferably contains a solvent. The solvent has the function of dispersing or dissolving each component. The solvent preferably contains water, and more preferably is only water. The solvent may also be a mixed solvent of water and an organic solvent for dispersing or dissolving each component. In this case, examples of the organic solvent used include acetone, acetonitrile, ethanol, methanol, isopropanol, glycerin, ethylene glycol, propylene glycol, triethanolamine, etc., which are organic solvents miscible with water. These organic solvents may also be used without mixing with water, and then mixed with water after dispersing or dissolving each component. These organic solvents may be used alone or in combination of two or more.

[0079] The water is preferably water that contains as little residue as possible from the viewpoint of preventing contamination of the polished object and inhibition of the action of other components. For example, water with a total transition metal ion content of 100 ppb or less is preferable. Here, the purity of the water can be increased by, for example, removing residual ions using an ion exchange resin, removing foreign matter using a filter, distillation, or other operations. Specifically, for example, deionized water (ion-exchanged water), pure water, ultrapure water, distilled water, etc. are preferably used.

[0080] <Anti-mold agent (preservative)> The post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) according to the present invention may further contain a fungicide (antiseptic). The post-CMP cleaning composition according to the present invention contains a nonionic polymer and is alkaline. For this reason, the post-CMP cleaning composition according to the present invention preferably contains a fungicide (antiseptic).

[0081] When the post-CMP cleaning composition according to the present invention contains a fungicide (preservative), the fungicide (preservative) that can be used is not particularly limited and can be appropriately selected depending on the type of nonionic polymer (component (A)). Specific examples include isothiazoline-based preservatives such as 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazol-3(2H)-one (BIT), and phenoxyethanol. Of these, isothiazoline-based preservatives are preferably used.

[0082] The above-mentioned antifungal agents (preservatives) may be used alone or in combination of two or more kinds.

[0083] The antifungal agent (preservative) may be synthetically produced or may be a commercially available product. Examples of commercially available products include the San-ai bag series such as San-ai bag R-30 (manufactured by San-ai Oburi Co., Ltd., an isothiazolinone compound), and Kordek MLX (manufactured by San-ai Oburi Co., Ltd.). TM MLX) (Nutrition & Biosciences Co., Ltd.), etc.

[0084] When the post-CMP cleaning composition contains an antifungal agent (preservative), the lower limit of the content (concentration) of the antifungal agent (preservative) is not particularly limited, but is preferably 0.0001% by mass or more, and more preferably 0.001% by mass or more. The upper limit of the content (concentration) of the antifungal agent (preservative) is not particularly limited, but is preferably 1% by mass or less, and more preferably 0.1% by mass or less. That is, the content (concentration) of the antifungal agent (preservative) in the post-CMP cleaning composition is preferably 0.0001% by mass or more and 1% by mass or less, more preferably 0.001% by mass or more and 0.1% by mass or less. Within such a range, a sufficient effect of inactivating or destroying microorganisms can be obtained. Note that, when the post-CMP cleaning composition contains two or more kinds of antifungal agents (preservatives), the above content refers to the total amount of these.

[0085] <Surfactant> The post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) according to the present invention may further contain a surfactant. The type of the surfactant is not particularly limited, and may be any of nonionic, anionic, cationic, and amphoteric surfactants.

[0086] Examples of nonionic surfactants include compounds other than the above-mentioned (A) component, such as alkyl ether type such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; alkyl phenyl ether type such as polyoxyethylene octylphenyl ether; alkyl ester type such as polyoxyethylene laurate; alkyl amine type such as polyoxyethylene lauryl amino ether; alkyl amide type such as polyoxyethylene lauric acid amide; polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; alkanolamide type such as oleic acid diethanolamide; allyl phenyl ether type such as polyoxyalkylene allyl phenyl ether. In addition, propylene glycol, diethylene glycol, monoethanolamine, alcohol ethoxylate, alkylphenol ethoxylate, tertiary acetylene glycol, alkanolamide, etc. can also be used as a nonionic surfactant. In addition, since the above-mentioned (A) component can function as a nonionic surfactant, it is not necessary to add a separate nonionic surfactant.

[0087] Examples of anionic surfactants include carboxylic acid types such as sodium myristate, sodium palmitate, sodium stearate, sodium laurate, and potassium laurate; sulfate types such as sodium octyl sulfate; phosphate types such as lauryl phosphoric acid and sodium lauryl phosphate; and sulfonic acid types such as sodium dioctyl sulfosuccinate and sodium dodecylbenzenesulfonate.

[0088] Examples of the cationic surfactant include amines such as laurylamine hydrochloride.

[0089] Examples of amphoteric surfactants include lecithin, alkylamine oxide, alkylbetaines such as N-alkyl-N,N-dimethylammonium betaine, and sulfobetaines.

[0090] The surfactant may be used alone or in combination of two or more kinds. In addition, the surfactant may be a commercially available product or a synthetic product.

[0091] When the post-CMP cleaning composition contains a surfactant, the lower limit of the surfactant content is preferably 0.01 mass% or more, and more preferably 0.05 mass% or more, based on the total mass of the post-CMP cleaning composition being 100 mass%. The upper limit of the surfactant content in the post-CMP cleaning composition is preferably 5 mass% or less, and more preferably 1 mass% or less, based on the total mass of the post-CMP cleaning composition being 100 mass%. When the post-CMP cleaning composition contains two or more surfactants, the surfactant content refers to the total amount of these.

[0092] From the viewpoint of further improving the effect of removing residues (foreign matter), it is preferable that the post-CMP cleaning composition according to the present invention is substantially free of surfactants (anionic surfactants and amphoteric surfactants). Here, "substantially free of surfactants" refers to a case where the content of surfactants (total content of anionic surfactants and amphoteric surfactants) relative to the entire post-CMP cleaning composition is less than 0.01 mass% (preferably less than 0.0005 mass%). That is, in one embodiment of the present invention, the content of surfactants is less than 0.01 mass% (preferably less than 0.0005 mass%) (lower limit: 0 mass%), with the total mass of the post-CMP cleaning composition being 100 mass% (relative to the post-CMP cleaning composition). From the viewpoint of further preventing the cause of foreign matter (residue), the post-CMP cleaning composition is free of anionic surfactants and amphoteric surfactants (total content of anionic surfactants and amphoteric surfactants = 0 mass%).

[0093] <Chelating agent> The post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) of the present invention may further include a chelating agent. The chelating agent may include an aminocarboxylic acid-based chelating agent and an organic phosphonic acid-based chelating agent. Examples of the aminocarboxylic acid-based chelating agent include ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, nitrilotriacetic acid, sodium nitrilotriacetate, ammonium nitrilotriacetate, diethylenetriaminepentaacetic acid, sodium diethylenetriaminepentaacetate, triethylenetetraminehexaacetic acid, and sodium triethylenetetraminehexaacetate. Examples of organic phosphonic acid chelating agents include 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid)(EDTPO), diethylenetriaminepenta(methylenephosphonic acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid.Of these, organic phosphonic acid chelating agents are more preferred. Among them, preferred are ethylenediaminetetrakis(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) and diethylenetriaminepentaacetic acid. Particularly preferred chelating agents are ethylenediaminetetrakis(methylenephosphonic acid) and diethylenetriaminepenta(methylenephosphonic acid).

[0094] The chelating agent may be used alone or in combination of two or more kinds. In addition, the chelating agent may be a commercially available product or a synthetic product.

[0095] When the post-CMP cleaning composition contains a chelating agent, the lower limit of the content of the chelating agent is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and even more preferably 0.002% by mass or more, based on the total mass of the post-CMP cleaning composition being 100% by mass. The upper limit of the content of the chelating agent is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.3% by mass or less, and particularly preferably 0.15% by mass or less. Note that when the post-CMP cleaning composition contains two or more types of chelating agents, the content of the chelating agents refers to the total amount of these.

[0096] From the viewpoint of further improving the effect of removing residues (foreign matter), it is preferable that the post-CMP cleaning composition according to the present invention is substantially free of a chelating agent. Here, "substantially free of a chelating agent" refers to a case where the content of the chelating agent (the total amount of the chelating agents when a plurality of chelating agents are included) is less than 0.01 mass% (preferably less than 0.0005 mass%) relative to the entire post-CMP cleaning composition. That is, in one embodiment of the present invention, the content of the chelating agent is less than 0.01 mass% (preferably less than 0.0005 mass%) (lower limit: 0 mass%), with the total mass of the post-CMP cleaning composition being 100 mass% (relative to the post-CMP cleaning composition). From the viewpoint of further preventing the cause of foreign matter (residue), the post-CMP cleaning composition is free of a chelating agent (content of the chelating agent = 0 mass%).

[0097] <Other additives> The post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) according to one embodiment of the present invention may contain other additives in any ratio as necessary within the range that does not impair the effects of the present invention. However, it is desirable to add as few components as possible other than the essential components of the post-CMP cleaning composition according to one embodiment of the present invention, since they may cause foreign matter (residues). Therefore, it is preferable to add as few other additives as possible. Examples of other additives include dissolved gases, reducing agents, oxidizing agents, etc.

[0098] In order to further improve the effect of removing residues (foreign matter), the post-chemical mechanical polishing cleaning composition ((post-CMP cleaning composition)) according to the present invention preferably contains substantially no abrasive grains. Here, "substantially no abrasive grains" refers to a case where the content of abrasive grains in the entire post-CMP cleaning composition is less than 0.01 mass %. That is, in one embodiment of the present invention, the content of abrasive grains is less than 0.01 mass % (lower limit: 0 mass %), with the total mass of the post-CMP cleaning composition being 100 mass % (relative to the post-CMP cleaning composition). From the viewpoint of further preventing the cause of foreign matter (residue), the post-CMP cleaning composition does not contain abrasive grains (content = 0 mass %).

[0099] Alternatively or in addition to the above, in order to further improve the effect of removing residues (foreign matter), the post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) according to the present invention preferably does not substantially contain particles having a particle diameter of 0.1 to 0.3 μm. Here, "substantially does not contain particles having a particle diameter of 0.1 to 0.3 μm" refers to the case where the number of particles having a particle diameter of 0.1 to 0.3 μm present in the post-CMP cleaning composition is less than 30 (preferably less than 10, more preferably less than 5). That is, in one embodiment of the present invention, the number of particles having a particle diameter of 0.1 to 0.3 μm present in the post-CMP cleaning composition is less than 30 (preferably less than 10, more preferably less than 5). From the viewpoint of further preventing the cause of foreign matter (residue), the post-CMP cleaning composition does not contain particles having a particle diameter of 0.1 to 0.3 μm (the number of particles = 0).

[0100] Alternatively or in addition to the above, in order to further improve the effect of removing residues (foreign matter), the post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) according to the present invention may further comprise a buffering agent, in particular a compound represented by the formula: A-COO - NH4 +(A is an alkyl group or a phenyl group having 1 to 10 carbon atoms) (ammonium monocarboxylate). Here, "substantially free of buffer" refers to a case where the content of buffer is less than 0.01 mass% relative to the entire post-CMP cleaning composition. That is, in one embodiment of the present invention, the content of buffer is less than 0.01 mass% (lower limit: 0 mass%), with the total mass of the post-CMP cleaning composition being 100 mass% (relative to the post-CMP cleaning composition). In one embodiment of the present invention, the post-CMP cleaning composition does not contain a buffer (content = 0 mass%). In one embodiment of the present invention, the post-CMP cleaning composition is a compound represented by the formula: A-COO - NH4 + The composition does not contain a buffer agent (ammonium monocarboxylate) represented by the formula (content = 0 mass %).

[0101] In one embodiment of the present invention, the post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) comprises a nonionic polymer (component (A)), a compound having an amino group and a hydroxyl group, and a fluorine-containing compound represented by the formula (1): H2N[(CH2) x NR 1 ] y R 2 and hexamethylenetetramine (component (B)), and at least one compound selected from the group consisting of a pH adjuster (component (C)), a fungicide (preservative), water, and an organic solvent. In one embodiment of the present invention, the post-CMP cleaning composition is substantially composed of a nonionic polymer (component (A)), a compound having an amino group and a hydroxyl group, a compound represented by the formula (1): H2N[(CH2) x NR 1 ] y R 2 and hexamethylenetetramine (component (B)), and at least one compound selected from the group consisting of a pH adjuster (component (C)), an isothiazolinone preservative, and water. In one embodiment of the present invention, the post-CMP cleaning composition is substantially composed of a nonionic polymer (component (A)), a compound represented by the formula (1): H2N[(CH2) x NR1 ] y R 2 and hexamethylenetetramine (component (B)), a pH adjuster (component (C)), an isothiazolinone preservative, and water. In one embodiment of the present invention, the post-CMP cleaning composition is substantially composed of a nonionic polymer (component (A)), a compound represented by the formula (1): H2N[(CH2) x NR 1 ] y R 2 (In formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrogen atom or a methyl group, x is 1 or more and 3 or less, and y is 1 or more and 5 or less), and hexamethylenetetramine (component (B)), a pH adjuster (component (C)), an isothiazolinone preservative, and water. In one embodiment of the present invention, the post-CMP cleaning composition is essentially composed of a nonionic polymer (component (A)), a compound represented by the formula (1): H2N[(CH2) x NR 1 ] y R 2 (In formula (1), R 1 is a hydrogen atom, and R 2 is a hydrogen atom, x is 2, and y is 1 or more and 3 or less) and hexamethylenetetramine (component (B)), a pH adjuster (component (C)), an isothiazolinone preservative, and water. In the above embodiment, "the post-CMP cleaning composition is substantially composed of X" means that the total content of X exceeds 99 mass% (upper limit: 100 mass%), with the total mass of the post-CMP cleaning composition being 100 mass% (relative to the post-CMP cleaning composition). Preferably, the post-CMP cleaning composition is composed of X (the above total content=100 mass%).

[0102] That is, in a preferred embodiment of the present invention, the post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) comprises a nonionic polymer (component (A)), a compound having an amino group and a hydroxyl group, a compound represented by the formula (1): H2N[(CH2) x NR 1 ] y R 2 and hexamethylenetetramine (component (B)), and at least one compound selected from the group consisting of a pH adjuster (component (C)), a fungicide (preservative), water, and an organic solvent (the total content above=100% by mass). In a preferred embodiment of the present invention, the post-CMP cleaning composition comprises a nonionic polymer (component (A)), a compound having an amino group and a hydroxyl group, and a compound represented by the formula (1): H2N[(CH2) x NR 1 ] y R 2 and hexamethylenetetramine (component (B)), and at least one compound selected from the group consisting of a pH adjuster (component (C)), an isothiazolinone preservative, and water (the total content above=100% by mass). In a preferred embodiment of the present invention, the post-CMP cleaning composition comprises a nonionic polymer (component (A)), a compound represented by the formula (1): H2N[(CH2) x NR 1 ] y R 2 and hexamethylenetetramine (component (B)), a pH adjuster (component (C)), an isothiazolinone preservative, and water (the total content above=100% by mass). In a preferred embodiment of the present invention, the post-CMP cleaning composition comprises a nonionic polymer (component (A)), a compound represented by the formula (1): H2N[(CH2) x NR 1 ] y R 2 (In formula (1), R 1 is a hydrogen atom or a methyl group, and R 2is a hydrogen atom or a methyl group, x is 1 or more and 3 or less, and y is 1 or more and 5 or less), and hexamethylenetetramine (component (B)), a pH adjuster (component (C)), an isothiazolinone preservative, and water (the total content of the above=100% by mass). In a preferred embodiment of the present invention, the post-CMP cleaning composition is composed of a nonionic polymer (component (A)), a compound represented by the formula (1): H2N[(CH2) x NR 1 ] y R 2 (In formula (1), R 1 is a hydrogen atom, and R 2 is a hydrogen atom, x is 2, and y is 1 or more and 3 or less) and hexamethylenetetramine (component (B)), a pH adjuster (component (C)), an isothiazolinone preservative, and water (the total content of the above=100% by mass).

[0103] The electrical conductivity (EC) of the post-chemical mechanical polishing cleaning composition of the present invention is preferably 0.1 mS / cm or more and less than 1.5 mS / cm, more preferably 0.2 mS / cm or more and less than 1.3 mS / cm. The electrical conductivity of the post-chemical mechanical polishing cleaning composition is within the above range, so that the desired effect of the present invention can be efficiently achieved. The electrical conductivity (EC) of the post-chemical mechanical polishing cleaning composition is the value measured according to the method described in the examples.

[0104] <Method of Manufacturing Post-Chemical Mechanical Polishing Cleaning Composition> The method for producing the post chemical mechanical polishing cleaning composition according to the present invention is not particularly limited, and may be, for example, a method for producing the post chemical mechanical polishing cleaning composition according to the present invention by mixing a nonionic polymer (component (A)) and a compound having an amino group and a hydroxyl group, the compound having the formula (1): H2N[(CH2) x NR 1 ] y R 2and hexamethylenetetramine, and other additives added as necessary. The details of each component are as described above. The temperature at which each component is mixed is not particularly limited, but is preferably 10°C or higher and 40°C or lower, and heating may be used to increase the dissolution rate. The mixing time is also not particularly limited.

[0105] [Post-chemical mechanical polishing cleaning treatment (surface treatment) method] According to the post-CMP cleaning composition of the present invention, the residues remaining on the surface of the polished object can be sufficiently removed (the number of residues remaining on the surface of the polished object after CMP can be effectively reduced). In addition, the surface roughness of the polished object (particularly, the polished substrate having silicon-silicon bonds) can be reduced. Therefore, the present invention provides a post-chemical mechanical polishing cleaning method, which includes subjecting the polished object to a post-chemical mechanical polishing cleaning treatment (surface treatment) using the post-CMP cleaning composition of the present invention. Here, the polished object may include a material (silicon material) containing silicon-silicon bonds. That is, the present invention provides a post-chemical mechanical polishing cleaning method, which uses the post-chemical mechanical polishing cleaning composition of the present invention to subject a polished object having silicon-silicon bonds to a post-chemical mechanical polishing cleaning treatment (surface treatment) to reduce residues on the surface of the polished object. In this specification, the term "post-chemical mechanical polishing cleaning method" refers to a method for reducing residues on the surface of a polished object, and is a method for performing cleaning in a broad sense. In this specification, the "post-chemical mechanical polishing cleaning treatment" is also simply referred to as "post-CMP cleaning treatment".

[0106] According to the post-CMP cleaning method of the present invention, the residue remaining on the surface of the polished object can be sufficiently removed. That is, the present invention provides a method for reducing the residue on the surface of the polished object, which comprises performing a post-CMP cleaning process on the polished object including a material (silicon material) containing silicon-silicon bonds using the post-chemical mechanical polishing cleaning composition of the present invention.

[0107] The post-CMP cleaning treatment method according to the present invention is carried out by directly contacting the post-CMP cleaning composition according to the present invention with the polished object.

[0108] The post-CMP cleaning method mainly includes (I) a method using a rinse polishing process and (II) a method using a cleaning process. That is, in one embodiment of the present invention, the post-chemical mechanical polishing cleaning method is a rinse polishing process or a cleaning process (the post-chemical mechanical polishing cleaning process is performed by a rinse polishing process or a cleaning process). The rinse polishing process and the cleaning process are performed to remove foreign matter (abrasive grain (particle) residues, organic residues such as polymers and pad debris, metal contaminants, etc.) on the surface of the polished object to obtain a clean surface. The above (I) and (II) will be described below.

[0109] (I) Rinse polishing treatment The post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) according to the present invention is preferably used in a rinse polishing process. That is, the post-CMP cleaning composition according to the present invention can be preferably used as a rinse polishing composition. The rinse polishing process is carried out on a polishing table (platen) to which a polishing pad is attached, after a polished object is polished by performing a final polishing (finish polishing) on ​​the object to be polished to obtain a polished object. In this case, the rinse polishing process is carried out by directly contacting the post-CMP cleaning composition according to the present invention with the polished object to be polished. As a result, the foreign matter on the surface of the polished object to be polished is removed by the frictional force (physical action) of the polishing pad and the chemical action of the post-CMP cleaning composition. Among the foreign matter, abrasive grain (particle) residues and organic residues are particularly easily removed by physical action. Therefore, in the rinse polishing process, the friction with the polishing pad on the polishing table (platen) can be used to effectively remove the abrasive grain (particle) residues and organic residues. Here, in the post-CMP cleaning process using the post-CMP cleaning composition according to the present invention, the polished object surface can be etched by the frictional force (physical action) of the polishing pad and the chemical action of the post-CMP cleaning composition. In addition, since the abrasive grain residue and organic residue are removed during this etching, the efficiency of reducing these residues is further improved. In addition, since the surface of the polished object is etched uniformly, the surface roughness can also be reduced.

[0110] That is, in this specification, the terms "rinse polishing treatment," "rinse polishing method," and "rinse polishing step" refer to a treatment, a method, and a step, respectively, for reducing residues on the surface of an object to be subjected to post-CMP cleaning treatment using a polishing pad.

[0111] Specifically, the rinse polishing process can be carried out by placing the polished surface of the object to be polished after the polishing process on a polishing table (platen) of a polishing apparatus, contacting the polishing pad with the polished semiconductor substrate, and supplying the post-CMP cleaning composition to the contact area while sliding the polished object to be polished and the polishing pad relative to one another.

[0112] As a polishing device, a general polishing device can be used which is equipped with a holder for holding the object to be polished and a motor whose rotation speed can be changed, and has a polishing platen onto which a polishing pad (polishing cloth) can be attached. In addition, the polishing apparatus is preferably equipped with a nozzle for discharging the post-CMP cleaning composition in addition to a nozzle for discharging the polishing composition. The operating conditions of the polishing apparatus during the rinse polishing process are not particularly limited, and can be appropriately set by a person skilled in the art.

[0113] The rinse polishing process can be carried out using either a single-sided polishing machine or a double-sided polishing machine. The polishing pad may be made of any material, including general nonwoven fabric, polyurethane, and porous fluororesin, without any particular limitations. The polishing pad is preferably provided with grooves for storing the post-CMP cleaning composition.

[0114] There are no particular limitations on the rinse polishing conditions. For example, the rotation speed of the polishing plate and the head (carrier) are 10 rpm (0.17 s -1 ) or more 100rpm(1.67s -1 ) or less, and the pressure applied to the polished object (polishing pressure) is preferably 0.5 psi (3.4 kPa) or more and 10 psi (68.9 kPa) or less. The method of supplying the post-CMP cleaning composition to the polishing pad is not particularly limited, and for example, a method of continuously supplying the composition using a pump or the like (flowing over) is used. There is no limit to the amount of supply, but it is preferable that the surface of the polishing pad is always covered with the post-CMP cleaning composition, and the supply rate is preferably 10 mL / min or more and 5000 mL / min or less. The rinse polishing time is also not particularly limited, but it is preferably 5 seconds or more and 180 seconds or less.

[0115] After the rinse polishing treatment with the post-CMP cleaning composition of the present invention, the polished object (object to be surface-treated) is preferably pulled up and removed while being sprayed with the post-CMP cleaning composition of the present invention.

[0116] (II) Cleaning treatment The post-chemical mechanical polishing cleaning composition (post-CMP cleaning composition) according to the present invention may be used in a cleaning process. That is, the post-CMP cleaning composition according to the present invention can be preferably used as a cleaning composition. The cleaning process is preferably carried out for the purpose of removing foreign matter on the surface of the polished object (cleaned object) after the final polishing (finish polishing) of the object to be polished is performed, after the above-mentioned rinse polishing process is performed, or after another rinse polishing process using a rinse polishing composition other than the post-CMP cleaning composition according to the present invention is performed to obtain a polished object to be polished (cleaned object). The cleaning process and the above-mentioned rinse polishing process are classified according to the location where these processes are performed, and the cleaning process is a post-CMP cleaning process (surface treatment) performed at a location other than the polishing table (platen), and is preferably a post-CMP cleaning process (surface treatment) performed after the polished object to be polished is removed from the polishing table (platen). In the cleaning process, the post-CMP cleaning composition according to the present invention can be directly contacted with the polished object to be polished to remove foreign matter on the surface of the object.

[0117] Examples of the method for performing the cleaning treatment include (i) a method in which a cleaning brush is brought into contact with one or both sides of a polished object while holding the polished object, and the surface of the object is rubbed with the cleaning brush while a post-CMP cleaning composition is supplied to the contact portion, and (ii) a method in which the polished object is immersed in the post-CMP cleaning composition and subjected to ultrasonic treatment or stirring (dip type), etc. In such a method, foreign matter on the surface of the polished object is removed by the frictional force of the cleaning brush or the mechanical force generated by the ultrasonic treatment or stirring, and the chemical action of the post-CMP cleaning composition.

[0118] In the above method (i), the method of bringing the post-CMP cleaning composition into contact with the polished object to be polished is not particularly limited, but examples include a spin type in which the polished object is rotated at high speed while the post-CMP cleaning composition is flowed from a nozzle onto the polished object, and a spray type in which the post-CMP cleaning composition is sprayed onto the polished object to clean it.

[0119] From the viewpoint of more efficient decontamination in a short time, it is preferable to adopt a spin or spray type cleaning process, and the spin type is more preferable.

[0120] Apparatuses for carrying out such cleaning treatment include batch-type cleaning apparatuses that simultaneously perform post-CMP cleaning treatment (surface treatment) on multiple polished objects housed in a cassette, and single-wafer cleaning apparatuses that perform post-CMP cleaning treatment (surface treatment) on one polished object mounted on a holder, etc. From the viewpoint of shortening the cleaning time, etc., a method using a single-wafer cleaning apparatus is preferable.

[0121] Furthermore, as an apparatus for carrying out the cleaning process, there is a polishing apparatus equipped with a cleaning device for scrubbing the polished object with a cleaning brush after removing the polished object from the polishing table (platen). By using such a polishing apparatus, the cleaning process of the polished object can be carried out more efficiently.

[0122] As such a polishing device, a general polishing device having a holder for holding a polished object, a motor capable of changing the rotation speed, a cleaning brush, etc. can be used. As the polishing device, either a single-sided polishing device or a double-sided polishing device can be used. When a rinse polishing process is performed after the CMP process, it is more efficient and preferable to perform the cleaning process using the same device as the polishing device used in the rinse polishing process.

[0123] The cleaning brush is not particularly limited, but is preferably a resin brush. The material of the resin brush is not particularly limited, but is preferably PVA (polyvinyl alcohol). More preferably, the cleaning brush is a PVA sponge.

[0124] There are no particular limitations on the cleaning conditions, and they can be set appropriately depending on the type of surface treatment object (polished object) and the type and amount of residue to be removed. For example, the rotation speed of the cleaning brush is 10 rpm (0.17 s -1 ) or more 200rpm(3.33s -1) or less, and the rotation speed of the object to be cleaned is 10 rpm (0.17 s -1 ) or more 100rpm(1.67s -1 ) or less. There is no particular restriction on the method of supplying the post-CMP cleaning composition to the cleaning brush, and for example, a method of continuously supplying the composition using a pump or the like (flowing over) is employed. There is no particular restriction on the amount of supply, but it is preferable that the cleaning brush and the surface of the object to be cleaned are always covered with the post-CMP cleaning composition, and the supply rate is preferably 10 mL / min or more and 5000 mL / min or less. There is no particular restriction on the cleaning time, but it is preferably 5 seconds or more and 180 seconds or less for the step using the post-CMP cleaning composition according to one embodiment of the present invention. If the supply rate is within such a range, foreign matter can be removed more effectively.

[0125] The temperature of the post-CMP cleaning composition during cleaning is not particularly limited and may usually be room temperature, but may be heated to about 40° C. or higher and 70° C. or lower within a range that does not impair performance.

[0126] In the above method (ii), the conditions for the cleaning method by immersion are not particularly limited, and any known method can be used.

[0127] Before carrying out the post-CMP cleaning treatment (surface treatment) by the above method (I) or (II), cleaning with water may be carried out.

[0128] (Post-cleaning process) As a post-CMP cleaning (surface treatment) method, it is preferable to further clean the polished object after the post-CMP cleaning (I) or (II) using the post-CMP cleaning composition according to the present invention. In this specification, this cleaning is referred to as a post-cleaning. The post-cleaning is not particularly limited, but examples thereof include a method of simply pouring water over the object to be surface-treated, a method of simply immersing the object to be surface-treated in water, and the like. As with the post-CMP cleaning by the method (II) described above, examples of the method include a method of contacting one or both sides of the object to be surface-treated with a cleaning brush while holding the object to be surface-treated, and rubbing the surface of the object to be surface-treated with a cleaning brush while supplying water or an aqueous solution (e.g., an NH3 aqueous solution) to the contact portion or while supplying water and an aqueous solution (e.g., an NH3 aqueous solution) in any order (supplying water and then supplying an aqueous solution, or supplying an aqueous solution and then supplying water), (brush cleaning), and a method of immersing the object to be surface-treated in water and performing ultrasonic treatment or stirring (dip type). Among these, a preferred method is to hold the object and bring the cleaning brush into contact with one or both sides of the object, and scrub the surface of the object with the cleaning brush while supplying water or an aqueous solution (e.g., an NH3 aqueous solution) to the contact area, or while supplying water and an aqueous solution (e.g., an NH3 aqueous solution) in any order (supplying water and then the aqueous solution, or supplying an NH3 aqueous solution and then water). Note that the apparatus and conditions for the post-cleaning process can be found in the description of the post-CMP cleaning process in (II) above. Here, it is particularly preferred to use deionized water as the water used in the post-cleaning process.

[0129] By carrying out a post-CMP cleaning treatment with the post-CMP cleaning composition according to one embodiment of the present invention, the residues are made extremely easy to remove, and therefore, by carrying out a post-CMP cleaning treatment (surface treatment) with the post-CMP cleaning composition according to one embodiment of the present invention and then carrying out a further cleaning treatment with water, the residues are extremely well removed.

[0130] [Method of manufacturing semiconductor substrate] The post-CMP cleaning method according to the present invention is preferably applied when the polished object is a polished semiconductor substrate. That is, the present invention also provides a method for producing a semiconductor substrate, the method comprising the steps of: subjecting the polished object to the polishing of the polished semiconductor substrate to the post-CMP cleaning method described above to reduce residues on the surface of the polished semiconductor substrate.

[0131] In this case, the polished object preferably contains a material (silicon material) containing silicon-silicon bonds. That is, the present invention also provides a method for producing a semiconductor substrate, comprising: a polishing step in which the polished object is a polished semiconductor substrate, a polishing composition containing abrasive grains is used to polish a pre-polished semiconductor substrate containing a material (silicon material) containing silicon-silicon bonds, thereby obtaining a polished semiconductor substrate; and a post-chemical mechanical polishing cleaning treatment step in which the post-chemical mechanical polishing cleaning composition according to the present invention is used to reduce residues containing the abrasive grains on the surface of the polished semiconductor substrate.

[0132] Details of the semiconductor substrate to which this manufacturing method is applied are as described above for the polished object to be subjected to post-CMP cleaning treatment (surface treatment) with the post-CMP cleaning composition.

[0133] In addition, the manufacturing method of a semiconductor substrate is not particularly limited as long as it includes a step of performing a post-CMP cleaning treatment on the surface of a polished semiconductor substrate using the post-CMP cleaning composition of the present invention (post-CMP cleaning treatment step). For example, such a manufacturing method includes a method having a polishing step and a cleaning step for forming a polished semiconductor substrate. Another example includes a method having a rinse polishing step between the polishing step and the cleaning step in addition to the polishing step and the cleaning step. Each of these steps will be described below.

[0134] <Polishing process> A polishing step that can be included in the method for manufacturing a semiconductor substrate is a step of polishing a semiconductor substrate to form a polished semiconductor substrate.

[0135] The polishing step is a chemical mechanical polishing (CMP) step. The polishing step may be a single step or a multiple step. Examples of the multiple step polishing step include a preliminary polishing step (rough polishing step) followed by a finish polishing step, and a primary polishing step followed by one or more secondary polishing steps followed by a finish polishing step. The post-CMP cleaning process using the post-CMP cleaning composition according to the present invention is preferably carried out after the finish polishing step.

[0136] As the polishing composition, a known polishing composition can be appropriately used according to the characteristics of semiconductor substrate.As the polishing composition, there is no particular limitation, but for example, the polishing composition containing abrasive grains, water-soluble polymer, pH adjuster, and solvent can be mentioned.

[0137] As the polishing device, a general polishing device can be used that is equipped with a holder for holding the object to be polished, a motor capable of changing the rotation speed, etc., and a polishing platen to which a polishing pad (polishing cloth) can be attached. As the polishing device, either a single-sided polishing device or a double-sided polishing device may be used.

[0138] <Post-chemical mechanical polishing cleaning (post-CMP cleaning, surface treatment) process> The post-chemical mechanical polishing cleaning process refers to a process of reducing residues on the surface of the polished object by using the post-chemical mechanical polishing cleaning composition of the present invention.In the manufacturing method of semiconductor substrate, after the rinse polishing process, a cleaning process as a post-CMP cleaning process may be carried out, or only the rinse polishing process or only the cleaning process may be carried out.

[0139] (Rinse polishing process) The rinse polishing process may be provided between the polishing process and the cleaning process in the method for manufacturing a semiconductor substrate. The rinse polishing process is a process for reducing foreign matter on the surface of a polished object (polished semiconductor substrate) by a post-CMP cleaning process method (rinse polishing process method) according to one embodiment of the present invention.

[0140] The details of the rinse polishing method used in the rinse polishing step are as described above in the explanation of the rinse polishing treatment.

[0141] (Cleaning process) In the method for manufacturing a semiconductor substrate, the cleaning step may be performed after the polishing step or after the rinse polishing step. The cleaning step is a step for reducing foreign matter on the surface of a polished object (polished semiconductor substrate) by a post-CMP cleaning treatment method (cleaning method) according to one embodiment of the present invention.

[0142] The details of the cleaning method used in the cleaning step are the same as those described above in (post-cleaning treatment).

[0143] Although the embodiments of the present invention have been described in detail, it is apparent that the same are illustrative and exemplary, not restrictive, and the scope of the present invention should be interpreted by the appended claims.

[0144] The present invention encompasses the following aspects and configurations.

[0145] 1. A post-chemical mechanical polishing cleaning composition comprising the following components (A) and (B) and having a pH of greater than 7.0 and not greater than 10.0: Component (A): Nonionic polymer Component (B): at least one compound selected from the group consisting of a compound having an amino group and a hydroxyl group, a compound represented by the following formula (1), and hexamethylenetetramine: Formula (1): H2N[(CH2) x NR 1 ] y R 2 In the formula (1), R1 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; each x is independently an integer of 1 to 10; and y is an integer of 1 to 8; 2. The post chemical mechanical polishing cleaning composition according to 1 above, wherein the component (A) contains at least one nonionic polymer selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, poly N-vinylacetamide, polyethylene glycol, hydroxyethyl cellulose and butenediol-vinyl alcohol copolymer, or is at least one compound selected from the above group; 3. The post-chemical mechanical polishing cleaning composition according to 1. or 2. above, wherein the component (A) contains at least one nonionic polymer selected from the group consisting of polyvinyl alcohol, polyethylene glycol, hydroxyethyl cellulose and butenediol-vinyl alcohol copolymer, or is at least one compound selected from the above group; 4. A post chemical mechanical polishing cleaning composition according to any one of 1. to 3. above, in which the component (B) contains at least one compound selected from the group consisting of 2-aminoethanol, 3-amino-1-propanol, diethanolamine, 2-(2-aminoethylamino)ethanol, 2-(methylamino)ethanol, 2-(2-aminoethoxy)ethanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, a compound represented by the above formula (1), and hexamethylenetetramine, or is at least one compound selected from the above group; 5. A post chemical mechanical polishing cleaning composition according to any one of 1. to 3. above, wherein the component (B) contains at least one compound selected from the group consisting of 2-aminoethanol, 3-amino-1-propanol, 2-(2-aminoethylamino)ethanol, 2-(methylamino)ethanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, a compound represented by the above formula (1), and hexamethylenetetramine, or is at least one compound selected from the above group; 6. The post chemical mechanical polishing cleaning composition according to any one of 1. to 3. above, wherein the component (B) contains at least one compound selected from the group consisting of the compound represented by the formula (1) above and hexamethylenetetramine, or is at least one compound selected from the above group; 7. The compound represented by the above formula (1) is R 1 is a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, and R 2 the post chemical mechanical polishing cleaning composition according to any one of 4. to 6. above, which is a compound represented by formula (1) in which is a hydrogen atom, a methyl group, an ethyl group or an n-propyl group, x is 1 or more and 5 or less, and y is 1 or more and 8 or less; 8. The compound represented by the above formula (1) is R 1 is a hydrogen atom or a methyl group, and R 2 the post chemical mechanical polishing cleaning composition according to any one of 4. to 6. above, which is a compound represented by formula (1) in which x is a hydrogen atom or a methyl group, y is 1 or more and 3 or less, and y is 1 or more and 5 or less; 9. The compound represented by the above formula (1) is R 1 is a hydrogen atom, and R 2 the post chemical mechanical polishing cleaning composition according to any one of 4. to 6. above, which is a compound represented by formula (1) in which is a hydrogen atom, x is 2, and y is 1 or more and 3 or less; 10. Formula: A-COO - NH4 +(A is an alkyl group or a phenyl group having 1 to 10 carbon atoms); 11. A post-chemical mechanical polishing cleaning composition according to any one of 1. to 10. above, which is essentially composed of the component (A), the component (B), and at least one member selected from the group consisting of a pH adjuster, an isothiazolinone preservative, and water; 12. A post-chemical mechanical polishing cleaning composition according to any one of 1. to 10. above, which consists of only the component (A), the component (B), and at least one selected from the group consisting of a pH adjuster, an isothiazolinone preservative, and water; 13. A post-chemical mechanical abrasive cleaning treatment method, comprising subjecting a polished object having silicon-silicon bonds to a post-chemical mechanical abrasive cleaning treatment using the post-chemical mechanical abrasive cleaning composition according to any one of 1. to 12. above, thereby reducing residues on the surface of the polished object; 14. The post-chemical mechanical polishing cleaning treatment method according to claim 13, which is a rinse polishing treatment method or a cleaning treatment method; 15. The polished object is a polished semiconductor substrate; A polishing step of obtaining a polished semiconductor substrate by polishing an unpolished semiconductor substrate having silicon-silicon bonds with a polishing composition containing abrasive grains; a post-chemical mechanical polishing cleaning treatment step of reducing the abrasive-containing residue on the surface of the polished semiconductor substrate using the post-chemical mechanical polishing cleaning composition according to any one of 1. to 12. above; A method for manufacturing a semiconductor substrate comprising the steps of: EXAMPLES

[0146] The present invention will be described in more detail using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. Unless otherwise specified, "%" and "parts" mean "% by mass" and "parts by mass", respectively. In the following examples, unless otherwise specified, the operations were performed under the conditions of room temperature (25°C) / relative humidity of 40% RH or more and 50% RH or less.

[0147] [Preparation of components (A)-(D)] The following components (A) to (D) were prepared.

[0148] <Component (A): Nonionic polymer> Polyvinyl alcohol (PVA) (product name JMR (registered trademark)-10HH, manufactured by Nippon Vinyl Acetate & Poval Co., Ltd.; Mw = 10,000) <Component (B): Amino group-containing compound> Hexamethylenetetramine (Tokyo Chemical Industry Co., Ltd.; molecular weight 140) Ethylenediamine (Tokyo Chemical Industry Co., Ltd.; molecular weight 60) Diethylenetriamine (Tokyo Chemical Industry Co., Ltd.; molecular weight 103) Triethylenetetramine (Tokyo Chemical Industry Co., Ltd.; molecular weight 146) 2-Aminoethanol (Tokyo Chemical Industry Co., Ltd.; molecular weight 61) 3-Amino-1-propanol (Tokyo Chemical Industry Co., Ltd.; molecular weight 75) 2-(2-aminoethylamino)ethanol (Tokyo Chemical Industry Co., Ltd.; molecular weight 104) 2-Amino-1,2-propanediol (Tokyo Chemical Industry Co., Ltd.; molecular weight 91) 2-(2-aminoethoxy)ethanol (Tokyo Chemical Industry Co., Ltd.; molecular weight 105) 2-Amino-2-ethyl-1,3-propanediol (Tokyo Chemical Industry Co., Ltd.; molecular weight 119) 2-(Methylamino)ethanol (Tokyo Chemical Industry Co., Ltd.; molecular weight 75) Diethanolamine (Tokyo Chemical Industry Co., Ltd.; molecular weight 105) 3-Amino-1,2-propanediol (Tokyo Chemical Industry Co., Ltd.; molecular weight 91) <Component (B'): Other amino group-containing compounds> Ammonium acetate (Kanto Chemical Co., Ltd.; molecular weight 77) Tetramethylammonium hydroxide (Tokyo Chemical Industry Co., Ltd.; molecular weight 91) Tetrabutylammonium hydroxide (Tokyo Chemical Industry Co., Ltd.; molecular weight 259) Ethylamine (Tokyo Chemical Industry Co., Ltd. product name: 33 wt% ethylamine aqueous solution; molecular weight: 45) <Component (C): pH buffer> Ammonia (Kanto Chemical Co., Ltd. product name: EL ammonia water (NH3 concentration: 28.0% to 30.0%); molecular weight 17) Acetic acid (Kanto Chemical Co., Ltd., product name: acetic acid; molecular weight: 60) Nitric acid (Kanto Chemical Co., Ltd. product name: nitric acid 69%; molecular weight: 63) Potassium hydroxide (Kanto Chemical Co., Ltd. product name: 48% potassium hydroxide aqueous solution; molecular weight: 56).

[0149] [Measurement of weight average molecular weight (Mw)] The weight average molecular weight (Mw) of the component (A) was measured by gel permeation chromatography (GPC) using the weight average molecular weight (converted into polyethylene glycol). The weight average molecular weight was measured using the following apparatus and conditions: GPC equipment: Shimadzu Corporation Model: Prominence + ELSD detector (ELSD-LTII) Column: VP-ODS (Shimadzu Corporation) Mobile phase A:MeOH B: 1% acetic acid solution Flow rate: 1mL / min Detector: ELSD temp. 40℃, Gain 8, N2GAS 350kPa Oven temperature: 40℃ Injection volume: 40μL.

[0150] [Measurement of electrical conductivity (EC)] The electrical conductivity of the post chemical mechanical polishing cleaning composition was measured using a tabletop electrical conductivity meter (manufactured by Horiba, Ltd., model number: DS-71).

[0151] [Measurement of pH of Post-Chemical Mechanical Polishing Cleaning Composition] The pH of the post-chemical mechanical polishing cleaning composition (liquid temperature: 25° C.) was confirmed using a pH meter (manufactured by Horiba, Ltd., product name: LAQUA (registered trademark)). The pH of the polishing composition described below was also measured by the same method.

[0152] Preparation of Post-Chemical Mechanical Polishing Cleaning Composition (Post-CMP Cleaning Composition) Example 1 Post-CMP cleaning composition 1 was prepared by mixing and stirring polyvinyl alcohol (PVA) (Mw=10,000) as component (A), hexamethylenetetramine as component (B), ammonia as component (C), and distilled water as a solvent at 25° C. for 5 minutes.

[0153] The content of each component was as follows: relative to the total amount of the post-CMP cleaning composition 1, the content of component (A) was 0.06 mass % (0.6 g / L), the content of component (B) was 0.100 mass % (7.1 mM), and the content of component (C) (pH adjuster) was an amount such that the pH of the post-CMP cleaning composition 1 was 9.2.

[0154] (Examples 2 to 20, Comparative Examples 1 to 13) Post-CMP cleaning compositions 2 to 33 were prepared in the same manner as in Example 1, except that the component (A), the component (B) / (B'), the component (C) and the pH were changed as shown in Table 1. The concentrations of the components (B) / (B') in the post-CMP cleaning compositions 2 to 20 and 22 to 33 were set to 7.1 mM, and the concentration of the components (B) / (B') in the post-CMP cleaning composition 21 was set to 3.7 mM.

[0155] The post-CMP cleaning compositions 1 to 33 prepared above do not contain abrasive grains (abrasive grain content=0 mass %).

[0156] [Table 1-1]

[0157] [Table 1-2]

[0158] [Preparation of polished object] A polished amorphous silicon substrate was prepared after being polished by the following chemical mechanical polishing (CMP) process.

[0159] (CMP process) As an object to be polished, a silicon wafer (amorphous silicon substrate) (300 mm wafer, manufactured by Advanced Materials Technology Corp.) having an amorphous silicon film of 2000 Å thick formed on its surface by CVD was prepared.

[0160] The amorphous silicon substrate prepared above was polished under the conditions below using a polishing composition having the following composition, to obtain a polished object (polished amorphous silicon substrate).

[0161] <Polishing composition> First, a silica slurry having the following composition was prepared: Colloidal silica (average primary particle size: 35 nm, average secondary particle size: 70 nm) 2.5% by mass Polyvinylpyrrolidone (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Pitzcol (registered trademark) K30A;Mw=45,000) 0.0625% by mass Ammonia (Kanto Chemical Co., Ltd. product name: EL ammonia water (NH3 concentration: 28.0% to 30.0%)) 0.0825% by mass (as NH3) Solvent: Distilled water.

[0162] The resulting polishing composition had a pH of 10.0.

[0163] <Polishing equipment and polishing conditions> Polishing equipment: REFLEXION (registered trademark) LK (manufactured by Applied Materials) Polishing pad: Anchor Techno Co., Ltd., polyurethane foam pad IC1010 Conditioner (dresser): Diamond pad conditioner (3M, 3M-A165 Conditioner Disk) Polishing pressure: 1.0 psi (1 psi = 6894.76 Pa, same below) Polishing platen rotation speed: 83 rpm Head rotation speed: 77 rpm Supply of polishing composition: free-flowing Polishing composition supply amount: 200mL / min Polishing time: 30 seconds.

[0164] [Rinse polishing process] After the surface of the object to be polished (amorphous silicon substrate) was polished in the above CMP process, the polished object to be polished (polished amorphous silicon substrate) was removed from the polishing table (platen). Next, in the same polishing apparatus, the polished object to be polished was mounted on another polishing table (platen), and the polished surface of the object to be polished was subjected to a rinse polishing treatment using each of the post-CMP cleaning compositions 1 to 33 under the following conditions.

[0165] <Rinse polishing device and rinse polishing conditions> Polishing equipment: REFLEXION (registered trademark) LK (manufactured by Applied Materials) Polishing pad: Fujibo Ehime Co., Ltd. Polyurethane foam pad H800 Type-1 (3-1S) Conditioner (dresser): 3M, nylon brush Grinding pressure: 1.0psi Plate rotation speed: 83 rpm Head rotation speed: 77 rpm Post-CMP cleaning composition supply: flow-through Post-CMP cleaning composition feed rate: 300 mL / min Polishing time: 60 seconds.

[0166] [Post-cleaning process] After the rinse-polishing process, the substrate surface was brush-cleaned using a 0.3% NH3 aqueous solution for 30 seconds, and then rinsed with deionized water for 20 seconds to obtain rinse-polished objects (rinse-polished amorphous silicon substrates 1-33 using post-CMP cleaning compositions 1-33 of the examples and comparative examples).

[0167] [evaluation] (Residue evaluation) Using an optical inspection machine Surfscan (registered trademark) SP5 manufactured by KLA-Tencor Corporation, the number of residues on the surface of the rinse-polished polished objects (rinse-polished amorphous silicon substrates 1 to 33) was evaluated.

[0168] Specifically, the number of residues with a diameter of more than 40 nm was counted for the remaining portion excluding the 3 mm wide portion from the outer peripheral edge of one side of the rinsed and polished amorphous silicon substrate (the region from 0 mm to 3 mm when the outer peripheral edge is set to 0 mm). After that, the number of abrasive grain residues and the number of organic residues for the rinsed and polished amorphous silicon substrate were measured by SEM observation using Review SEM RS6000 manufactured by Hitachi High-Tech Corporation. First, the number of residues present in the remaining portion excluding the 5 mm wide portion from the outer peripheral edge of one side of the rinsed and polished amorphous silicon substrate was counted by SEM observation. Next, the type of residue (abrasive grain or organic residue) was determined by visual SEM observation, and the number of abrasive grain residues (SiO2 residues) and organic residues (pad dust, polymer, etc.) was measured.

[0169] The total number of residues (the sum of the number of abrasive grain residues and the number of organic residues) is preferably as small as possible. As an example, a total number of residues of 29 or less is acceptable, preferably 25 or less, more preferably 19 or less, and particularly preferably 15 or less.

[0170] It is preferable that the number of abrasive grain residues (SiO2 residues) is as small as possible. As an example, the number of abrasive grain residues (SiO2 residues) is acceptable if it is 15 or less, preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less.

[0171] In addition, it is preferable that the number of organic residues (such as pad debris and polymers) is as small as possible. As an example, the number of organic residues (such as pad debris and polymers) is acceptable if it is 10 or less, preferably 9 or less, more preferably 8 or less, and particularly preferably 7 or less.

[0172] The results of each of the above evaluations are shown in Table 2 below.

[0173] [Table 2]

[0174] As is clear from Table 2 above, the post-CMP cleaning compositions of the Examples can more efficiently remove residues from amorphous silicon substrates than the post-CMP cleaning compositions of the Comparative Examples. The above results are the results of evaluation immediately after the production of the post-CMP cleaning compositions, but in the case of long-term storage or preservation, it is preferable to contain a preservative (anti-fungal agent). The preservative (anti-fungal agent) has little or no effect on the above results. For this reason, it is considered that a post-CMP cleaning composition containing a preservative (anti-fungal agent) will also produce the same results as above.

Claims

1. A post-chemical mechanical polishing cleaning composition comprising the following components (A) and (B) and having a pH of more than 7.0 and not more than 10.0: Component (A): Nonionic polymer Component (B): at least one compound selected from the group consisting of a compound having an amino group and a hydroxyl group, a compound represented by the following formula (1), and hexamethylenetetramine: Formula (1): H ２ N[(CH ２ ) ｘ NR １ ] ｙ R ２ In the formula (1), R １ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; each x is independently an integer of 1 to 10; and y is an integer of 1 to 8.

2. 2. The post chemical mechanical polishing cleaning composition of claim 1, wherein the component (A) comprises at least one nonionic polymer selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, poly N-vinylacetamide, polyethylene glycol, hydroxyethyl cellulose, and butenediol-vinyl alcohol copolymer.

3. 2. The post chemical mechanical polishing cleaning composition according to claim 1, wherein the component (B) comprises at least one compound selected from the group consisting of the compound represented by formula (1) and hexamethylenetetramine.

4. Formula: A-COO － N.H. ４ ＋ 2. The post chemical mechanical polishing cleaning composition of claim 1, which does not contain a buffer represented by the formula: (A is an alkyl group or a phenyl group having 1 to 10 carbon atoms).

5. The post-chemical mechanical polishing cleaning composition according to claim 1, which is essentially composed of the component (A), the component (B), and at least one selected from the group consisting of a pH adjuster, an isothiazolinone preservative, and water.

6. A post-chemical mechanical abrasive cleaning method, comprising subjecting a polished object having silicon-silicon bonds to a post-chemical mechanical abrasive cleaning treatment using the post-chemical mechanical abrasive cleaning composition according to any one of claims 1 to 5, thereby reducing residues on the surface of the polished object.

7. 7. The post chemical mechanical polishing cleaning process of claim 6, which is a rinse polishing process or a cleaning process.

8. the polished object is a polished semiconductor substrate; A polishing step of obtaining a polished semiconductor substrate by polishing an unpolished semiconductor substrate having silicon-silicon bonds with a polishing composition containing abrasive grains; A post-chemical mechanical polishing cleaning treatment step of reducing the abrasive-containing residue on the polished semiconductor substrate surface using the post-chemical mechanical polishing cleaning composition according to any one of claims 1 to 5; A method for manufacturing a semiconductor substrate comprising the steps of:

Images