Composition for chemical mechanical polishing and polishing method

Abstract

Provided are: a composition for chemical mechanical polishing, with which it is possible to increase the polishing rate of a molybdenum film and to reduce corrosion of the molybdenum film; and a polishing method which uses the composition for chemical mechanical polishing.　The composition for chemical mechanical polishing according to the present invention contains (A) abrasive grains, (B) a compound which has a partial structure represented by formula (1) in each molecule, and (F) a liquid medium, and has a pH of 1 to 5 inclusive. (In the formula (1), R1 and R2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R3 represents an alkyl group having 8 to 20 carbon atoms. X- represents at least one selected from the group consisting of alkyl sulfonate, fluorosulfonate, toluene sulfonate, styrene sulfonate, alkyl sulfone imide, trifluoromethane sulfone imide, Br-, Cl-, SCN-, PF6 -, BF4 -, and trifluoroacetate. * represents a bonding site.)

Description

Chemical mechanical polishing composition and polishing method

[0001] The present invention relates to a chemical mechanical polishing composition and a polishing method using the same.

[0002] With advancements in semiconductor integrated circuit manufacturing technology, there is a growing demand for higher integration and faster operation of semiconductor devices. Consequently, the flatness of the semiconductor substrate surface required in the manufacturing process of fine circuits in semiconductor devices is becoming increasingly stringent, making chemical mechanical polishing (CMP) an indispensable technology in semiconductor device manufacturing.

[0003] In semiconductor substrates manufactured via CMP, tungsten, which has excellent filling properties, has been widely used for via holes that electrically connect wiring in the vertical direction. Chemical mechanical polishing compositions for polishing such tungsten films have been proposed (see, for example, Patent Document 1). On the other hand, in recent years, the use of molybdenum instead of tungsten has been considered to improve the resistance increase of tungsten wiring due to miniaturization. Chemical mechanical polishing compositions for polishing such molybdenum films have been proposed (see, for example, Patent Document 2).

[0004] Japanese Patent Publication No. 2008-503875, International Publication No. 2013 / 188296

[0005] In CMP (Chemical Mechanical Polishing) for forming molybdenum via holes, it is necessary to polish the molybdenum film deposited on the silicon oxide film at high speed to remove and flatten the areas other than the molybdenum filling the via holes. To achieve this, a chemical mechanical polishing composition with a high polishing speed for the molybdenum film is required. Furthermore, because molybdenum is more easily oxidized than tungsten, corrosion is more likely to occur in CMP, and there has been a problem in that conventional tungsten polishing compositions cannot be directly applied.

[0006] Some aspects of the present invention provide a chemical mechanical polishing composition and a polishing method using the same, which can increase the polishing speed of a molybdenum film and reduce corrosion of a molybdenum film in CMP of a semiconductor wafer containing a molybdenum film.

[0007] One aspect of the chemical mechanical polishing composition according to the present invention contains: (A) abrasive grains; (B) a compound having, in one molecule, a partial structure represented by the following formula (1); and (F) a liquid medium, and has a pH of 1 or more and 5 or less. (In formula (1), R １ and R ２ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R ３ represents an alkyl group having 8 to 20 carbon atoms. X － represents at least one selected from the group consisting of alkyl sulfonate, fluorosulfonate, toluenesulfonate, styrene sulfonate, alkyl sulfonimide, trifluoromethane sulfonimide, Br － , Cl － , SCN － , PF ６ － , BF ４ － and trifluoroacetate. * represents a binding site.)

[0008] In one aspect of the chemical mechanical polishing composition, the component (B) may be a compound having, in one molecule, the partial structure represented by formula (1) and a tertiary amine structure.

[0009] In any aspect of the chemical mechanical polishing composition, the composition may further contain at least one selected from the group consisting of (C) an iron(III) compound and (D) an oxidizing agent.

[0010] In any aspect of the chemical mechanical polishing composition, the composition may further contain: (C) an iron(III) compound; and (E) a compound having 1 to 3 of at least one functional group selected from the group consisting of an amino group and salts thereof.

[0011] In any aspect of the chemical mechanical polishing composition, the total amine value of the component (E) may be 0 to 320 mgKOH / g.

[0012] In any aspect of the chemical mechanical polishing composition, the average secondary particle diameter of the component (A) may be 10 nm to 120 nm.

[0013] In any embodiment of the chemical mechanical polishing composition, the content of component (A) may be 0.1% to 5% by mass when the total mass of the chemical mechanical polishing composition is 100% by mass.

[0014] Any embodiment of the chemical mechanical polishing composition may be used to polish a surface having at least one of a molybdenum film and a tungsten film.

[0015] One embodiment of the polishing method according to the present invention includes the step of polishing a surface to be polished having at least one of a molybdenum film and a tungsten film using a chemical mechanical polishing composition according to any of the above embodiments.

[0016] One embodiment of the compound according to the present invention is the compound represented by the following formula (2). (In formula (2), R ４ X represents an alkyl group with 12 to 20 carbon atoms. － These include alkyl sulfonates, fluorosulfonates, toluene sulfonates, styrene sulfonates, alkyl sulfonimides, trifluoromethanesulfonimides, and Br. － , Cl － SCN － , PF ６ － BF ４ － (This represents at least one selected from the group consisting of trifluoroacetates.)

[0017] According to the chemical mechanical polishing composition of the present invention, in CMP of a semiconductor wafer containing a molybdenum film, the polishing speed of the molybdenum film can be increased and the corrosion of the molybdenum film can be reduced.

[0018] Figure 1 is a schematic cross-sectional view showing a workpiece suitable for use in the polishing method according to this embodiment. Figure 2 is a schematic cross-sectional view showing the polishing method according to this embodiment. Figure 3 is a schematic perspective view showing a chemical mechanical polishing apparatus.

[0019] Preferred embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below, and includes various modifications that do not alter the essence of the invention.

[0020] In this specification, numerical ranges described as "X to Y" are interpreted as including the numerical value X as the lower limit and the numerical value Y as the upper limit.

[0021] 1. Chemical mechanical polishing composition The chemical mechanical polishing composition according to one embodiment of the present invention contains (A) abrasive grains (hereinafter also referred to as "component (A)"), (B) a compound having a substructure represented by the following formula (1) in one molecule (hereinafter also referred to as "component (B)"), and (F) a liquid medium (hereinafter also referred to as "component (F)"), and has a pH of 1 or more and 5 or less. (In formula (1), R １ and R ２ Each of these independently represents a hydrocarbon group having 1 to 6 carbon atoms, R ３ X represents an alkyl group with 8 to 20 carbon atoms. － These include alkyl sulfonates, fluorosulfonates, toluene sulfonates, styrene sulfonates, alkyl sulfonimides, trifluoromethanesulfonimides, and Br. － , Cl － SCN － , PF ６ － BF ４ － This represents at least one selected from the group consisting of trifluoroacetates. (* indicates a binding site.)

[0022] The following describes in detail each component that may be included in the chemical mechanical polishing composition according to this embodiment.

[0023] 1.1. Component (A) The chemical mechanical polishing composition according to this embodiment contains abrasive particles (A). Component (A) can be inorganic particles such as silica, ceria, alumina, zirconia, and titania, but silica is preferred. Examples of silica include fumed silica and colloidal silica, but colloidal silica is preferred. As colloidal silica, for example, one manufactured by the method described in Japanese Patent Application Publication No. 2003-109921 can be used.

[0024] (A) In the case of silica particles whose main component is silica, other components may also be included. Examples of other components include aluminum compounds and silicon compounds. By further including aluminum compounds or silicon compounds in the silica particles, the surface hardness of the silica particles can be reduced, which may allow for a more stable polishing speed while further reducing the occurrence of polishing scratches and dishing on the polished surface.

[0025] Examples of aluminum compounds include aluminum hydroxide, aluminum oxide (alumina), aluminum chloride, aluminum nitride, aluminum acetate, aluminum phosphate, aluminum sulfate, sodium aluminate, and potassium aluminate. On the other hand, examples of silicon compounds include silicon nitride, silicon carbide, silicates, silicones, and silicon resins.

[0026] The shape of component (A) is not particularly limited and may be spherical, cocoon-shaped, chain-spherical, or have multiple protrusions on its surface. Abrasive grains having multiple protrusions on their surface can be manufactured, for example, by applying the methods described in Japanese Patent Application Publication No. 2007-153732 or Japanese Patent Application Publication No. 2013-121631.

[0027] The zeta potential of component (A) in the chemical mechanical polishing composition is preferably -40 mV or higher, more preferably -30 mV or higher, even more preferably -20 mV or higher, and particularly preferably -10 mV or higher, from the viewpoint of improving dispersion stability by suppressing crosslinking and aggregation with component (B). The zeta potential of component (A) in the chemical mechanical polishing composition is preferably 40 mV or lower, more preferably 30 mV or lower, even more preferably 20 mV or lower, and particularly preferably 10 mV or lower, from the viewpoint of suppressing the number of defects in the molybdenum film.

[0028] (A) The absolute value of the zeta potential of component (A) is preferably 2 mV to 40 mV, and more preferably 3 mV to 30 mV, from the viewpoint of improving dispersion stability and suppressing the number of defects in the molybdenum film. Examples of zeta potential measuring devices include the "ELSZ-2000ZS" manufactured by Otsuka Electronics Co., Ltd., the "Zetasizer Ultra" manufactured by Malvern, and the "DT300" manufactured by Dispersion Technology Inc.

[0029] Component (A) may have at least a portion of its surface modified with functional groups. Component (A) with at least a portion of its surface modified with functional groups has a larger absolute value of zeta potential and an increased electrostatic repulsion force between components (A) compared to component (A) that is not surface-modified with functional groups. As a result, the dispersion stability of component (A) in the chemical mechanical polishing composition is improved, and component (A) becomes less likely to localize on the surface of the molybdenum film, thus enabling a practical polishing speed for the molybdenum film while reducing the amount of molybdenum film being dished.

[0030] (A) Component may have a functional group represented by the following general formula (3): -SO ３ － M ＋ (3) (M ＋ (This represents a monovalent cation.)

[0031] In the above general formula (3), M ＋ The monovalent cations represented by are not limited to these, but for example, H ＋ Li ＋Na ＋ _K ＋ NH ４ ＋ These are examples. In other words, the functional group represented by the above general formula (3) can also be rephrased as "at least one functional group selected from the group consisting of sulfo groups and salts thereof." Here, "salt of a sulfo group" refers to a sulfo group (-SO ３ The hydrogen ions contained in H) ＋ Na ＋ _K ＋ NH ４ ＋ This refers to a functional group substituted with a monovalent cation such as the above. Component (A) having the functional group represented by the above general formula (3) is an abrasive grain in which the functional group represented by the above general formula (3) is fixed to its surface via covalent bonds, and does not include abrasive grains in which a compound having the functional group represented by the above general formula (3) is physically or ionically adsorbed to its surface.

[0032] Component (A), having the functional group represented by the above general formula (3), can be produced, for example, as follows. First, silica particles prepared by a known method and a mercapto group-containing silane coupling agent are thoroughly stirred in an acidic medium to covalently bond the mercapto group-containing silane coupling agent to the surface of the silica particles. Examples of the mercapto group-containing silane coupling agent include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. Next, a suitable amount of hydrogen peroxide is added and allowed to stand for a sufficient amount of time to obtain component (A), having the functional group represented by the above general formula (3).

[0033] (A) Component may have a functional group represented by the following general formula (4): -COO － M ＋ (4) (M ＋ (This represents a monovalent cation.)

[0034] In the above general formula (4), M ＋ The monovalent cations represented by are not limited to these, but for example, H ＋ Li ＋ Na ＋_K ＋ NH ４ ＋ The following are examples. In other words, the functional group represented by the above general formula (4) can also be rephrased as "at least one functional group selected from the group consisting of carboxyl groups and salts thereof." Here, "salt of a carboxyl group" means a salt in which the hydrogen ions contained in the carboxyl group (-COOH) are Li ＋ Na ＋ _K ＋ NH ４ ＋ This refers to a functional group substituted with a monovalent cation such as the above. Component (A) having the functional group represented by the above general formula (4) is an abrasive grain in which the functional group represented by the above general formula (4) is fixed to its surface via covalent bonds, and does not include abrasive grains in which a compound having the functional group represented by the above general formula (4) is physically or ionically adsorbed to its surface.

[0035] Component (A), having the functional group represented by the above general formula (4), can be produced, for example, as follows. First, silica particles prepared by a known method and a carboxylic acid anhydride-containing silane coupling agent are thoroughly stirred in a basic medium to covalently bond the carboxylic acid anhydride-containing silane coupling agent to the surface of the silica particles. Further hydrolysis of the modified carboxylic acid anhydride is performed to undergo a ring-opening reaction to a dicarboxylic acid, thereby obtaining abrasive grains having the functional group represented by the above general formula (4). Here, examples of carboxylic acid anhydride-containing silane coupling agents include 3-(triethoxysilyl)propyl succinic anhydride.

[0036] (A) Component may have a functional group represented by the following general formula (5) and / or the following general formula (6). -NR ５ R ６ (5) -N ＋ R ５ R ６ R ７ M － (6) (In formulas (5) and (6) above, R ５ , R ６ and R ７ Each of these independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.－ (This represents a monovalent anion.)

[0037] The functional group represented by the above general formula (5) represents an amino group, and the functional group represented by the above general formula (6) represents a salt of an amino group. Therefore, the functional group represented by the above general formula (5) and the functional group represented by the above general formula (6) can be collectively rephrased as "at least one functional group selected from the group consisting of amino groups and salts thereof." Component (A) having the functional group represented by the above general formula (5) and / or the above general formula (6) is an abrasive grain on which the functional group represented by the above general formula (5) and / or the above general formula (6) is fixed to its surface via covalent bonds, and does not include abrasive grains on which a compound having the functional group represented by the above general formula (5) and / or the above general formula (6) is physically or ionically adsorbed to its surface.

[0038] In the above general formula (6), M － The monovalent anions represented by are not limited to these, but for example, OH － F － , Cl － , Br － , I － , CN － In addition to anions such as those mentioned above, anions derived from acidic compounds can also be cited.

[0039] In the above general formulas (5) and (6), R ５ ~R ７ Each of these independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, but R ５ ~R ７ Two or more of these may be bonded together to form a ring structure.

[0040] R ５ ~R ７ The hydrocarbon group represented by may be any of the following: an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aromatic aliphatic hydrocarbon group, or an alicyclic hydrocarbon group. Furthermore, the aliphatic group of the aliphatic hydrocarbon group and the aromatic aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched. Examples of these hydrocarbon groups include linear, branched, or cyclic alkyl groups, alkenyl groups, aralkyl groups, and aryl groups.

[0041] Component (A) having the functional group represented by the above general formula (5) and / or the above general formula (6) can be produced, for example, as follows. First, silica particles prepared by a known method and an amino group-containing silane coupling agent are thoroughly stirred in an acidic medium, and the amino group-containing silane coupling agent is covalently bonded to the surface of the silica particles, thereby producing component (A) having the functional group represented by the above general formula (5) and / or the above general formula (6). Examples of amino group-containing silane coupling agents include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

[0042] The average secondary particle diameter of component (A) is obtained by measuring and converting the scattered light intensity of the chemical mechanical polishing composition using a particle size distribution analyzer based on dynamic light scattering. The average secondary particle diameter of component (A) measured by this method is preferably 120 nm or less, more preferably 110 nm or less, and particularly preferably 100 nm or less. The average secondary particle diameter of the abrasive grains (A) is preferably 10 nm or more, more preferably 15 nm or more, and particularly preferably 20 nm or more. When the average secondary particle diameter of component (A) is within the above range, a practical polishing speed for the molybdenum film is more easily achieved. Examples of particle size distribution analyzers include the "Zetasizer Ultra" manufactured by Malvern. Note that the average secondary particle diameter measured using dynamic light scattering represents the average particle diameter of secondary particles formed by the aggregation of primary particles.

[0043] The content of component (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more, when the total mass of the chemical mechanical polishing composition is 100% by mass. Furthermore, the content of component (A) is preferably 5% by mass or less, more preferably 4% by mass or less, and particularly preferably 3% by mass or less, when the total mass of the chemical mechanical polishing composition is 100% by mass. When the content of component (A) is within the above range, the polishing speed of the molybdenum film can be increased, and the occurrence of dishing due to excessive polishing of the molybdenum film can be reduced.

[0044] 1.2. Component (B) The chemical mechanical polishing composition according to the present embodiment contains (B) a compound having a partial structure represented by the following formula (1) in one molecule. (In formula (1), R １ and R ２ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R ３ represents an alkyl group having 8 to 20 carbon atoms. X － represents at least one selected from the group consisting of alkyl sulfonate, fluorosulfonate, toluene sulfonate, styrene sulfonate, alkyl sulfonimide, trifluoromethane sulfonimide, Br － , Cl － , SCN － , PF ６ － , BF ４ － and trifluoroacetate. * represents a binding site.)

[0045] Since the surface potential of a molybdenum film is negative when the pH is in the range of 1 or more and 5 or less, it is considered that component (B), which is positively charged during CMP, adsorbs in a large amount on the surface of the molybdenum film to form a protective film. As a result, it is considered that excessive corrosion of the molybdenum film is suppressed. On the other hand, when the pH is not 1 or more and 5 or less, component (B) cannot adsorb on the surface of the molybdenum film to form a protective film, and the surface of the molybdenum film is easily corroded during CMP, which is considered to cause polishing defects.

[0046] In the above formula (1), R １ and R ２Each of these is independently a hydrocarbon group having 1 to 6 carbon atoms, but hydrocarbon groups having 1 to 5 carbon atoms are preferred, hydrocarbon groups having 1 to 4 carbon atoms are more preferred, hydrocarbon groups having 1 to 3 carbon atoms are even more preferred, and hydrocarbon groups having 1 to 2 carbon atoms are particularly preferred. Examples of hydrocarbon groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, cyclohexyl group, vinyl group, allyl group, 1-propenyl group, 2-propenyl group, ethynyl group, propagyl group, phenyl group, and the like.

[0047] In the above formula (1), R ３ The alkyl group is an alkyl group having 8 to 20 carbon atoms, preferably an alkyl group having 9 to 16 carbon atoms, and more preferably an alkyl group having 10 to 14 carbon atoms. Examples of alkyl groups having 8 to 20 carbon atoms include octyl group, ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group.

[0048] In the above formula (1), X － The anions represented by are alkyl sulfonates, fluorosulfonates, toluene sulfonates, styrene sulfonates, alkyl sulfonimides, trifluoromethanesulfonimides, and Br. － , Cl － SCN － , PF ６ － BF ４ － It is at least one selected from the group consisting of and trifluoroacetates. Among these, bromide ions or chloride ions are preferred.

[0049] Furthermore, component (B) is preferably a compound having a substructure represented by formula (1) and a tertiary amine structure in a single molecule. The tertiary amine structure is preferably the structure represented by the following general formula (7). -NR ８ - (7) (In formula (2), R ８(This represents an alkyl group with 1 to 3 carbon atoms.)

[0050] Examples of component (B) include the compound represented by formula (8) below, the compound represented by formula (9) below, and the compound represented by formula (10) below. These components (B) may be used individually or in combination of two or more.

[0051] (In formula (8), R １ , R ２ , R ４ , R ５ and R ６ Each of these independently represents a methyl group, an ethyl group, a propyl group, or an isopropyl group. ３ X represents an alkyl group with 8 to 20 carbon atoms. － These include alkyl sulfonates, fluorosulfonates, toluene sulfonates, styrene sulfonates, alkyl sulfonimides, trifluoromethanesulfonimides, and Br. － , Cl － SCN － , PF ６ － BF ４ － (This represents at least one selected from the group consisting of trifluoroacetates. n represents an integer from 0 to 5.)

[0052] (In formula (9), R １ , R ２ , R ４ , R ５ and R ７ Each of these independently represents a methyl group, an ethyl group, a propyl group, or an isopropyl group. ３ and R ６ Each of these independently represents an alkyl group having 8 to 20 carbon atoms. － These include alkyl sulfonates, fluorosulfonates, toluene sulfonates, styrene sulfonates, alkyl sulfonimides, trifluoromethanesulfonimides, and Br. － , Cl － SCN － , PF ６ － BF ４ －(This represents at least one selected from the group consisting of trifluoroacetates. n represents an integer from 1 to 5.)

[0053] (In formula (10), R １ , R ２ , R ４ , R ５ and R ７ Each of these independently represents a methyl group, an ethyl group, a propyl group, or an isopropyl group. ３ and R ６ Each of these independently represents an alkyl group having 8 to 20 carbon atoms. ８ X represents an ethyl group, a propyl group, a propylene group, a propargyl group, or a vinylbenzyl group. － These include alkyl sulfonates, fluorosulfonates, toluene sulfonates, styrene sulfonates, alkyl sulfonimides, trifluoromethanesulfonimides, and Br. － , Cl － SCN － , PF ６ － BF ４ － (This represents at least one selected from the group consisting of trifluoroacetates. n represents an integer from 1 to 5.)

[0054] The total amine value of component (B) is preferably 0 mg KOH / g or more, more preferably 10 mg KOH / g or more, and particularly preferably 20 mg KOH / g or more. The total amine value of component (B) is preferably 320 mg KOH / g or less, more preferably 280 mg KOH / g or less, and particularly preferably 250 mg KOH / g or less. When the total amine value of component (B) is within the above range, excessive corrosion of the molybdenum film can be effectively suppressed.

[0055] The total amine value of component (B) is calculated by determining the total amount of primary, secondary, and tertiary amines contained in 1 g of component (B) from the amount of hydrochloric acid required to neutralize the total amount of primary, secondary, and tertiary amines in 1 g of component (B), and then converting that total amount to mg of potassium hydroxide. The total amine value of component (B) can be measured and calculated by a method in accordance with ASTM D 2073.

[0056] The content of component (B) is preferably 0.001% by mass or more, and more preferably 0.002% by mass or more, when the total mass of the chemical mechanical polishing composition is 100% by mass. The content of component (B) is preferably 0.1% by mass or less, and more preferably 0.05% by mass or less, when the total mass of the chemical mechanical polishing composition is 100% by mass. When the content of component (B) is within the above range, excessive corrosion of the molybdenum film can be effectively suppressed.

[0057] 1.3. Components (C) and (D) The chemical mechanical polishing composition according to this embodiment preferably further contains at least one selected from the group consisting of (C) an iron(III) compound (hereinafter also referred to as "component (C)") and (D) an oxidizing agent other than component (C) (hereinafter also referred to as "component (D)").

[0058] 1.3.1. Component (C) The chemical mechanical polishing composition according to this embodiment preferably contains component (C). Component (C) has the effect of oxidizing the surface of the molybdenum film to create a brittle modified layer, thereby promoting the polishing of the molybdenum film. In addition, the modified layer may have the effect of suppressing corrosion of the molybdenum film.

[0059] Component (C) may be either an organic iron(III) acid salt or an inorganic iron(III) acid salt, as long as it has the effects described above.

[0060] Specific examples of component (C) include iron(III) nitrate, iron(III) ammonium sulfate, iron(III) perchlorate, iron(III) chloride, iron(III) sulfate, iron(III) citrate, iron(III) ammonium citrate, and iron(III) ammonium oxalate. Of these components (C), iron(III) nitrate is particularly preferred. Component (C) may be used alone or in combination of two or more. Furthermore, since component (C) has the same effect as component (D), it may be used alone without being combined with component (D), or in combination with component (D).

[0061] The content of component (C) is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and particularly preferably 0.03% by mass or more, when the total mass of the chemical mechanical polishing composition is 100% by mass. From the viewpoint of suppressing corrosion of the molybdenum film, the content of component (C) 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, when the total mass of the chemical mechanical polishing composition is 100% by mass. When the content of component (C) is within the above range, it may be possible to polish the molybdenum film at high speed while suppressing corrosion of the molybdenum film.

[0062] 1.3.2. Component (D) The chemical mechanical polishing composition according to this embodiment may contain component (D). By including component (D), the effect of creating a fragile modified layer on the molybdenum film surface is promoted, and the polishing speed of the molybdenum film may be increased.

[0063] Examples of component (D) include hydrogen peroxide, peracetic acid, percarbonate, urea peroxide, perchloric acid, and persulfate (e.g., sodium persulfate, potassium persulfate, ammonium persulfate). Among these components (D), hydrogen peroxide is particularly preferred considering its oxidizing power, compatibility with component (C), and ease of handling. Component (D) may be used alone or in combination of two or more. Furthermore, since component (D) has the same effect as component (C), it may be used alone without combining it with component (C), or in combination with component (C).

[0064] The content of component (D) is preferably 0.01% by mass or more, and more preferably 0.02% by mass or more, when the total mass of the chemical mechanical polishing composition is 100% by mass. The content of component (D) is preferably 1% by mass or less, and more preferably 0.1% by mass or less, when the total mass of the chemical mechanical polishing composition is 100% by mass. When the content of component (D) is within the above range, it may be possible to polish the molybdenum film at high speed while suppressing corrosion of the molybdenum film.

[0065] 1.4. Component (E) The chemical mechanical polishing composition according to this embodiment preferably contains a compound having 1 to 3 of at least one functional group selected from the group consisting of amino groups and salts thereof (hereinafter also referred to as "component (E)"). Since it is difficult to sufficiently reduce the corrosion of the molybdenum film by using component (E) alone, it is preferable to use component (B) and component (E) in combination. By using component (B) and component (E) in combination, it may be possible to obtain an effect that synergistically reduces the corrosion of the molybdenum film while maintaining a high polishing speed of the molybdenum film. Furthermore, from the viewpoint of effectively improving the etching speed of the molybdenum film, it is also preferable to use component (C) and component (E) in combination.

[0066] Examples of amino groups and their salts include functional groups represented by the following general formula (5) or general formula (6). -NR ５ R ６ (5) -N ＋ R ５ R ６ R ７ M － (6) (In formulas (5) and (6) above, R ５ , R ６ and R ７ Each of these independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. － (This represents a monovalent anion.)

[0067] In the above general formulas (5) and (6), M － As a monovalent anion represented by , OH － F －, Cl － , Br － , I － NO ３ － , HCO ３ － These are some examples.

[0068] In the above general formulas (5) and (6), R ５ , R ６ and R ７ Each of these independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, but R ５ , R ６ and R ７ Two or more of them may be bonded together to form a ring structure. Also, R ５ , R ６ and R ７ If at least one of them is a substituted hydrocarbon group, the substituent is preferably a carboxyl group represented by the following general formula (11) and its salts.

[0069] - COO － M ＋ (11) (M ＋ (This represents a monovalent cation.)

[0070] In the above general formula (11), M ＋ The monovalent cations represented by are not limited to these, but for example, H ＋ Li ＋ Na ＋ _K ＋ NH ４ ＋ These are some examples.

[0071] R ５ ~R ７ The hydrocarbon group represented by may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aromatic aliphatic hydrocarbon group, or an alicyclic hydrocarbon group. Furthermore, the aliphatic group of the aliphatic hydrocarbon group and the aromatic aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched. Examples of these hydrocarbon groups include linear, branched, or cyclic alkyl groups, alkenyl groups, aralkyl groups, and aryl groups.

[0072] As the alkyl group, a lower alkyl group having 1 to 6 carbon atoms is preferred, and a lower alkyl group having 1 to 4 carbon atoms is more preferred. Examples of such alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, cyclopentyl group, and cyclohexyl group.

[0073] As the alkenyl group, a lower alkenyl group having 1 to 6 carbon atoms is preferred, and a lower alkenyl group having 1 to 4 carbon atoms is more preferred. Examples of such alkenyl groups include vinyl group, n-propenyl group, isopropenyl group, n-butenyl group, isobutenyl group, sec-butenyl group, tert-butenyl group, and the like.

[0074] The aralkyl group is preferably one having 7 to 12 carbon atoms. Examples of such aralkyl groups include benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylhexyl group, methylbenzyl group, methylphenethyl group, and ethylbenzyl group.

[0075] The aryl group is preferably one having 6 to 14 carbon atoms. Examples of such aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,5-xylyl, naphthyl, and anthyl groups.

[0076] The aromatic rings of the aryl group and the aralkyl group may have substituents such as lower alkyl groups like methyl or ethyl groups, halogen atoms, nitro groups, amino groups, or hydroxyl groups.

[0077] (E) The component is not particularly limited as long as it is a compound having 1 to 3 of at least one functional group selected from the group consisting of amino groups and salts thereof, but it is preferable that it has a structure represented by the following general formula (12) or the following general formula (13). -N(R ８N ＋ M － ) ｎ (R ９ ) ２－ｎ (12) -N(R ８ COO － M ＋ ) ｎ (R ９ ) ２－ｎ (13) (In formulas (12) and (13) above, R ８ Each of these independently represents a substituted or unsubstituted divalent hydrocarbon group. ９ Each of these independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. － M represents a monovalent anion. ＋ (where n represents a monovalent cation, and n is an integer between 1 and 2.)

[0078] In the above general formulas (12) and (13), R ８ Examples of divalent hydrocarbon groups represented by include alkanediyl groups having 1 to 3 carbon atoms. In the above general formulas (12) and (13), R ９ The hydrocarbon group represented is preferably an alkyl group having 10 or more carbon atoms. Examples of alkyl groups having 10 or more carbon atoms include decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc. In the above general formula (12), M － As a monovalent anion represented by , OH － F － , Cl － , Br － , I － NO ３ － , HCO ３ － Examples include the above general formula (13), M ＋ As a monovalent cation represented by , H ＋ Li ＋ Na ＋ _K ＋ NH ４ ＋ These are some examples.

[0079] Because component (E) has the structure represented by the above general formula (12) and / or the above general formula (13), the amino groups in component (E) are more easily adsorbed onto the surface of the molybdenum film, which may effectively reduce corrosion of the molybdenum portion. Furthermore, by further having a carboxyl group as in the structure represented by the above general formula (13), component (E) becomes more effectively adsorbed onto the surface of the molybdenum film, which may more effectively reduce corrosion.

[0080] Specific examples of component (E) include dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, N-methyloctadecylamine, N,N-dimethyldodecylamine, N-(2-{[2-(dodecylamino)ethyl]amino}ethyl)glycine, 2,6,10-trimethyl-2,6,10-triazaundecane, ethylenediaminetetraacetic acid, lauryliminodipropionate, myristyliminodipropionate, stearyliminodipropionate, palmityliminodipropionate, cocamidopropylamine oxide, benzyldimethylhexadecylammonium chloride, benzalkonium chloride, etc. These components (E) may be used individually or in combination of two or more.

[0081] The content of component (E) is preferably 0.01% by mass or more, and more preferably 0.02 parts by mass or more, when the total mass of the chemical mechanical polishing composition is 100% by mass. The content of component (E) is preferably 0.2% by mass or less, and more preferably 0.15% by mass or less, when the total mass of the chemical mechanical polishing composition is 100% by mass. When the content of component (E) is within the above range, the dispersion stability of component (A) may be improved by suppressing crosslinking and aggregation with component (A) while effectively reducing the corrosion of the molybdenum film.

[0082] 1.5. (F) Liquid Medium The chemical mechanical polishing composition according to this embodiment contains (F) liquid medium (also referred to as "component (F)" in this specification). Examples of component (F) include water, a mixed medium of water and alcohol, and a mixed medium containing water and an organic solvent that is compatible with water. Among these, it is preferable to use a mixed medium of water, water and alcohol, and it is more preferable to use water. Pure water can preferably be used as the raw material for water. Component (F) may be included as the remainder of the above-mentioned components.

[0083] 1.6. Other Components The chemical mechanical polishing composition according to this embodiment may contain, as necessary, additives such as acidic compounds, surfactants, water-soluble polymers, corrosion inhibitors, and pH adjusters, in addition to the components described above. The following describes each of the additives.

[0084] 1.6.1. Acidic Compounds The chemical mechanical polishing composition according to this embodiment may contain acidic compounds. Examples of acidic compounds include organic acids and inorganic acids. By including acidic compounds, (A) the polishing speed of the molybdenum film may be further increased through interaction with the abrasive grains.

[0085] Examples of organic acids include monocarboxylic acids such as lactic acid, glycolic acid, formic acid, acetic acid, benzoic acid, p-hydroxybenzoic acid, quinaldic acid, glycine, alanine, lysine, arginine, and tryptophan; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, aspartic acid, and glutamic acid; polycarboxylic acids such as citric acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, polyacrylic acid, and polymaleic acid; diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid; aromatic amino acids and heterocyclic amino acids other than those listed above; and amide sulfuric acid. These organic acids may also form salts. These organic acids may be used individually or in combination of two or more in any proportion.

[0086] Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. These inorganic acids may also form salts. These inorganic acids may be used individually or in combination of two or more in any proportion.

[0087] If an acidic compound is present, the content of the acidic compound is preferably 0.001 to 3% by mass, more preferably 0.002 to 2% by mass, and particularly preferably 0.003 to 1% by mass, when the total mass of the chemical mechanical polishing composition is considered to be 100% by mass.

[0088] 1.6.2. Surfactants The chemical mechanical polishing composition according to this embodiment may contain surfactants. By including surfactants, it may be possible to impart appropriate viscosity to the chemical mechanical polishing composition.

[0089] Examples of surfactants include anionic surfactants, cationic surfactants, and nonionic surfactants. Examples of anionic surfactants include fatty acid soaps, carboxylates such as alkyl ether carboxylates; sulfonates such as alkylbenzene sulfonates, alkylnaphthalene sulfonates, and α-olefin sulfonates; sulfates such as higher alcohol sulfates, alkyl ether sulfates, and polyoxyethylene alkylphenyl ether sulfates; and fluorine-containing surfactants such as perfluoroalkyl compounds. Examples of cationic surfactants include aliphatic amine salts and aliphatic ammonium salts. Examples of nonionic surfactants include nonionic surfactants having triple bonds such as acetylene glycol, acetylene glycol ethylene oxide adducts, and acetylene alcohol; and polyethylene glycol-type surfactants. These surfactants may be used individually or in combination of two or more.

[0090] If a surfactant is included, the surfactant content is preferably 0.001 to 5% by mass, more preferably 0.001 to 3% by mass, and particularly preferably 0.01 to 1% by mass, when the total mass of the chemical mechanical polishing composition is taken as 100% by mass.

[0091] 1.6.3. Water-soluble polymers The chemical mechanical polishing composition according to this embodiment may contain water-soluble polymers. By adsorbing the water-soluble polymer onto the surface to be polished and reducing polishing friction, it may be possible to reduce the occurrence of polishing defects such as dishing, erosion, and scratches on the surface to be polished.

[0092] Examples of such water-soluble polymers include polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine, polyvinyl methyl ether, polyallylamine, and hydroxyethylcellulose.

[0093] The weight-average molecular weight (Mw) of the water-soluble polymer is preferably 1,000 to 1,500,000, more preferably 10,000 to 500,000, and particularly preferably 30,000 to 100,000. When the weight-average molecular weight of the water-soluble polymer is within the above range, the water-soluble polymer is more easily adsorbed onto the polished surface, further reducing polishing friction. As a result, it may be possible to reduce the occurrence of polishing defects such as dishing, erosion, and scratches on the polished surface. In this specification, "weight-average molecular weight (Mw)" refers to the weight-average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography).

[0094] When a water-soluble polymer is included, the content of the water-soluble polymer is preferably 0.001 to 1% by mass, and more preferably 0.002 to 0.1% by mass, when the total mass of the chemical mechanical polishing composition is considered as 100% by mass. The content of the water-soluble polymer also depends on the weight-average molecular weight (Mw) of the water-soluble polymer, but it is preferable to adjust it so that the viscosity of the chemical mechanical polishing composition is less than 10 mPa·s. When the viscosity of the chemical mechanical polishing composition is less than 10 mPa·s, the molybdenum film can be polished at high speed, and because the viscosity is appropriate, the chemical mechanical polishing composition can be stably supplied onto the polishing cloth.

[0095] 1.6.4. Corrosion Inhibitors The chemical mechanical polishing composition according to this embodiment may contain a corrosion inhibitor. Examples of corrosion inhibitors include benzotriazole and its derivatives. Here, a benzotriazole derivative refers to a benzotriazole in which one or more hydrogen atoms are replaced with a carboxyl group, a methyl group, an amino group, a hydroxyl group, etc. Examples of benzotriazole derivatives include 4-carboxybenzotriazole and its salts, 7-carboxybenzotriazole and its salts, benzotriazole butyl ester, 1-hydroxymethylbenzotriazole, 1-hydroxybenzotriazole, etc.

[0096] If an anticorrosion agent is included, the amount of the anticorrosion agent is preferably 1% by mass or less, and more preferably 0.001 to 0.1% by mass, when the total mass of the chemical mechanical polishing composition is taken as 100% by mass.

[0097] 1.6.5. pH Adjusting Agents The chemical mechanical polishing composition according to this embodiment may further contain a pH adjusting agent in order to adjust the pH of the chemical mechanical polishing composition to a desired value. Examples of pH adjusting agents include acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and monocarboxylic acid, as well as basic compounds such as sodium hydroxide, potassium hydroxide, TMAH (tetramethylammonium hydroxide), and ammonia.

[0098] Furthermore, the pH of the chemical mechanical polishing composition according to this embodiment can be appropriately adjusted to be strongly acidic within the recommended pH range by the action of a catalyst such as component (C). By adjusting the amount of additive added according to the object to be polished, a polished surface with higher flatness can be obtained.

[0099] 1.7. pH The pH of the chemical mechanical polishing composition according to this embodiment is 1 or higher, preferably 1.5 or higher, and more preferably 2 or higher, from the viewpoint of the storage stability of component (A). The pH of the chemical mechanical polishing composition according to this embodiment is 5 or lower, preferably 4 or lower, and more preferably 3 or lower, from the viewpoint of effectively exhibiting the etching action of the molybdenum film. When the pH of the chemical mechanical polishing composition is within the above range, a chemical mechanical polishing composition is obtained that can achieve both the storage stability of component (A) and the effective etching action of the molybdenum film.

[0100] Furthermore, the pH of the chemical mechanical polishing composition can be adjusted, for example, by adding the pH adjusting agents mentioned above, and one or more of these can be used.

[0101] In this invention, pH refers to the hydrogen ion concentration, and its value can be measured using a commercially available pH meter (for example, a benchtop pH meter manufactured by Horiba, Ltd.).

[0102] 1.8. Applications The chemical mechanical polishing composition according to this embodiment can be used as an abrasive for polishing surfaces of multiple substrates constituting semiconductor devices, which have at least one of a molybdenum film and a tungsten film. For example, in a workpiece having an insulating film with contact holes and a molybdenum film and / or tungsten film provided in the contact holes and on the insulating film, it can be used in a process to polish the molybdenum film and / or tungsten film on the insulating film to form molybdenum plugs (Mo-plugs) and / or tungsten plugs (W-plugs) embedded in the contact holes in the insulating film.

[0103] 1.9. Method for Preparing the Chemical Mechanical Polishing Composition The chemical mechanical polishing composition according to this embodiment can be prepared by dissolving or dispersing the above-mentioned components in a liquid medium such as water. The method of dissolution or dispersion is not particularly limited, and any method that can be used as long as uniform dissolution or dispersion is achieved may be applied. Furthermore, there are no particular limitations on the mixing order or mixing method of the above-mentioned components.

[0104] Furthermore, the chemical mechanical polishing composition according to this embodiment can be prepared as a concentrated stock solution and diluted with a liquid medium such as water before use.

[0105] 2. Polishing Method A polishing method according to one embodiment of the present invention includes the step of polishing a surface to be polished having at least one of a molybdenum film and a tungsten film using the above-described chemical mechanical polishing composition. According to the chemical mechanical polishing composition of the present invention, the polishing speed of the molybdenum film and / or tungsten film can be increased, and the occurrence of corrosion on the molybdenum surface and / or tungsten surface can be reduced, so that molybdenum plugs and / or tungsten plugs of good quality can be formed. The polishing method according to this embodiment will be described in detail below with reference to Figures 1 to 3.

[0106] 2.1. Workpiece Figure 1 shows an example of a workpiece 100 to which the polishing method according to this embodiment is applied. The workpiece 100 is manufactured, for example, by going through the following steps (1) to (4).

[0107] (1) First, a substrate 10 is prepared as shown in Figure 1. The substrate 10 may be composed of, for example, a silicon substrate and a silicon oxide film formed thereon. Furthermore, functional devices such as transistors may be formed on the substrate 10.

[0108] (2) Next, a silicon oxide film 12, which is an insulating film, is formed on the substrate 10 by a CVD method using silane gas and oxygen gas. After that, the silicon oxide film 12 is polished partially by CMP to flatten the surface.

[0109] (3) Next, a resist pattern is formed on the silicon oxide film 12. Using this as a mask, the silicon oxide film 12 is etched to form contact holes 14. After forming the contact holes 14, the resist pattern is removed.

[0110] (4) Next, the CVD method is applied to deposit a molybdenum film 16 on the surface of the silicon oxide film 12 and inside the contact holes 14.

[0111] Through the above steps, the workpiece 100 is formed.

[0112] 2.2. Chemical Mechanical Polishing Process In the chemical mechanical polishing process, as shown in Figure 2, the molybdenum film 16 is polished using the chemical mechanical polishing composition of the present invention until the silicon oxide film 12 is exposed. The chemical mechanical polishing composition of the present invention allows for a high polishing speed of the molybdenum film and reduces the occurrence of corrosion on the molybdenum surface, thus enabling the formation of a molybdenum plug of good quality.

[0113] It is preferable to remove any abrasive particles remaining on the polished surface after the chemical mechanical polishing process. This removal of abrasive particles can be carried out by conventional cleaning methods. For example, after brush scrubbing, abrasive particles adhering to the polished surface can be removed by cleaning with an alkaline cleaning solution of approximately 1:1:5 (mass ratio) of ammonia:hydrogen peroxide:water. Furthermore, as a cleaning solution for impurity metal species adsorbed on the polished surface, for example, an aqueous solution of citric acid, a mixed aqueous solution of hydrofluoric acid and citric acid, or a mixed aqueous solution of hydrofluoric acid and ethylenediaminetetraacetic acid (EDTA) can be used.

[0114] 2.3. Chemical Mechanical Polishing Apparatus In the chemical mechanical polishing process described above, for example, a chemical mechanical polishing apparatus 200 as shown in Figure 3 can be used. Figure 3 is a schematic perspective view of the chemical mechanical polishing apparatus 200. The process is carried out by supplying slurry (composition for chemical mechanical polishing) 44 from a slurry supply nozzle 42 and rotating a turntable 48 to which a polishing pad 46 is attached, while bringing a carrier head 52 holding a semiconductor substrate 50 into contact with it. A water supply nozzle 54 and a dresser 56 are also shown in Figure 3.

[0115] The polishing load of the carrier head 52 can be selected within the range of 10 to 980 hPa, preferably 30 to 490 hPa. The rotational speed of the turntable 48 and the carrier head 52 can be appropriately selected within the range of 10 to 400 rpm, preferably 30 to 150 rpm. The flow rate of the slurry (chemical mechanical polishing composition) 44 supplied from the slurry supply nozzle 42 can be selected within the range of 10 to 1,000 mL / min, preferably 50 to 400 mL / min.

[0116] Examples of commercially available chemical polishing machines include those manufactured by Ebara Corporation, models "EPO-112," "EPO-222," and "F-REX300SII"; those manufactured by Lappmaster SFT, models "LGP-510" and "LGP-552"; those manufactured by Applied Materials, models "Mirra" and "Reflexion"; and those manufactured by G&P TECHNOLOGY, model "POLI-762."

[0117] 3. A novel compound according to one embodiment of the compound represented by the following formula (2) is the compound represented by the following formula (2).

[0118] In formula (2), R ４ X represents an alkyl group having 12 to 20 carbon atoms. Examples of alkyl groups having 12 to 20 carbon atoms include dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosanyl groups. In formula (2), X － Each of these is independently alkyl sulfonate, fluorosulfonate, toluene sulfonate, styrene sulfonate, alkyl sulfonimide, trifluoromethanesulfonimide, Br － , Cl － SCN － , PF ６ － BF ４ － It represents at least one selected from the group consisting of and trifluoroacetates.

[0119] The compound represented by formula (2) above can be synthesized by the method described in Synthesis Example 6 or Synthesis Example 7 later. １ H-NMR measurement and １３ - Chemical shift values ​​were determined using NMR measurements, and each compound was identified.

[0120] The compound synthesized in Synthesis Example 6 is N-(2-((2-((2-(Dodecyldimethyl-14-azaneyl)ethyl)(methyl)amino)ethyl)(methyl)amino)ethyl)-N,N-dimethyldodecan-1-aminium dibromide.

[0121] The compound synthesized in Synthesis Example 7 is N-(2-((2-((2-((Hexadecyldimethyl-14-azaneyl)ethyl)(methyl)amino)ethyl)(methyl)amino)ethyl)-N,N-dimethylhexadecan-1-aminium dibromide.

[0122] 4. Examples The present invention will be described below with reference to examples, but the present invention is not limited in any way by these examples. In these examples, "parts" and "%" are based on mass unless otherwise specified.

[0123] 4.1. Preparation of Silica Particle Aqueous Dispersion 4.1.1. Preparation of Aqueous Dispersion A A mother liquor was prepared by mixing 100 parts by mass of methanol, 11 parts by mass of ultrapure water, and 6 parts by mass of 28% ammonia water. To 100 parts by mass of methanol used in the mother liquor, 50 parts by mass of tetramethoxysilane and 14 parts by mass of methanol were mixed to prepare an alkoxysilane solution. A solution of alkaline catalyst was prepared by mixing 34 parts by mass of ultrapure water and 5 parts by mass of 28% ammonia water. The raw material solution and the alkaline catalyst solution were injected at a constant rate into the mother liquor over 60 minutes while maintaining the temperature of the mother liquor at 25°C to obtain the reaction solution. The alkaline catalyst concentration in the mother liquor was 0.68 mol / L. The alcohol concentration in the alkoxysilane solution was 6.5 mol / L. The total amount of water charged in the reaction system was 8.9 mol per 1 mol of tetramethoxysilane injected. To 100 parts by mass of the obtained reaction solution, 190 parts by mass of ultrapure water was added while heating to remove the solvent, thereby completely replacing the solvent component with water while maintaining a constant volume, and a colloidal silica dispersion was obtained. This colloidal silica dispersion was used as aqueous dispersion A. The average secondary particle diameter of the silica particles in aqueous dispersion A was measured to be 98 nm. The average secondary particle diameter of each silica particle in aqueous dispersions A to D was calculated from the scattered light intensity measured using a particle size distribution analyzer (Malvern, model "Zetasiser Ultra").

[0124] 4.1.2. Preparation of Aqueous Dispersion B PL-1 (manufactured by Fuso Chemical Industries, Ltd., 12% colloidal silica dispersion) was used as aqueous dispersion B. The average secondary particle size of the silica particles in aqueous dispersion B was measured to be 42 nm.

[0125] 4.1.3. Preparation of Aqueous Dispersion C PL-3 (manufactured by Fuso Chemical Industries, Ltd., 19.5% colloidal silica dispersion) was used as aqueous dispersion C. The average secondary particle size of the silica particles in aqueous dispersion C was measured to be 71 nm.

[0126] 4.1.4. Preparation of Aqueous Dispersion D 3250 g of PL-1 (Fuso Chemical Industries, Ltd., 12% colloidal silica dispersion) was mixed with 25% aqueous ammonia (Fujifilm Wako Pure Chemical Industries, Ltd.) to adjust the pH to 9. Then, 3.9 g of a (3-triethoxysilyl) mercapto group-containing silane coupling agent (product name "KBM-803", Shin-Etsu Chemical Co., Ltd.) was added dropwise, and the mixture was stirred at 60°C for 2 hours. Then, 50 g of hydrogen peroxide (Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the mixture was refluxed for 8 hours to obtain aqueous dispersion D containing silica particles surface-modified with sulfo groups. The average secondary particle size of the silica particles in aqueous dispersion D was measured to be 42 nm.

[0127] 4.2. Production of Component (B) 4.2.1. Synthesis Example 1 N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dimethyldodecan-1-aminium chloride, represented by the following formula (B-1), was synthesized as follows. 4.19 g (25 mmol) of 1,2,4-triazolechloromethyl, 5.34 g (25 mmol) of dimethyldodecylamine, and 28.6 g of acetonitrile were added to a 100 mL round-bottom flask equipped with a condenser bottle, and the mixture was heated and stirred at 83°C for 12 hours. After the reaction was complete, liquid-liquid washing was performed three times with n-hexane (50 mL) / acetonitrile (30 mL). The acetonitrile layer was collected and concentrated to obtain 9.2 g of a white solid. This was designated as (B-1). １ H-NMR measurement and １３ The chemical shift values ​​in the C-NMR measurements are as follows: 1 H NMR (400MHz, CDCl3) δ; 8.88 (Ph, d, 1H), 8.05 (Ph, d, 1H), 7.66 (Ph, m, 1H), 7.42 (Ph, m, 1H), 7.08 (CH2, s, 2H), 3.68 (CH2, m, 2H), 3.56 (CH3, s, 6H), 1.92 (CH2, br, 2H), 1.33-1.23 (CH2, br, 18H), 0.88 (CH3, t, 3H). 13C NMR (100MHz, CDCl3) δ; 145.3, 134.9, 130.5, 125.6, 120.1, 111.7, 69.9, 63.2, 48.9, 31.9, 29.6, 29.5, 29.4, 29.2, 26.3, 22.7, 14.2.

[0128] 4.2.2. Synthesis Example 2 N1-(2-(Hexadecyldimethyl-14-azaneyl)ethyl)-N1,N2,N2-trimethylethane-1,2-diamine bromide, represented by the following formula (B-2), was synthesized as follows. In a 100 mL three-necked flask equipped with a Limebloch glass and a dropping funnel, 5.2 g (30 mmol) of pentamethyldiethylenetriamine and 28.7 g of acetonitrile were heated at 83°C. 9.16 g (30 mmol) of bromohexadecane was added dropwise from the dropping funnel over 2 hours, and the mixture was heated and stirred for 3 hours. After the reaction was complete, the mixture was left overnight to allow the dionium salt to precipitate. The mixture was filtered through a Buchner funnel, and the filtrate was collected. The filtrate was concentrated, and the slurry was washed with 100 mL of cold n-hexane, and the mixture was stirred until a white solid settled. Decantation was performed, and the supernatant was removed. This process was repeated three times, and the white solid was collected. The mixture was concentrated under reduced pressure using an evaporator to obtain 3.46 g of a white viscous solid. This was designated as (B-2). １ H-NMR measurement and １３ The chemical shift values ​​in the C-NMR measurements are as follows: 1 H NMR (400MHz, CDCl3) δ; 3.83 (N + CH2, br, 2H), 3.81 (CH2, br, 2H), 3.47 (CH3, s, 6H), 2.5-2.21 (CH2, m, 16H), 1.76 (CH2, br, 2H), 1.36-1.25 (CH2, br, 26H), 0.88 (CH3, t, 3H).・ 13C NMR (100MHz, CDCl3) δ; 64.6, 60.4, 57.2, 55.5, 51.6, 48.7, 45.5, 42.7, 31.9, 29.8, 29.7, 29.6, 29.5, 29.4, 29.3, 26.4, 22.9, 22.7, 14.2

[0129] 4.2.3. Synthesis Example 3 N1-(2-(Dimethylamino)ethyl)-N2-(2-(hexadecyldimethyl-14-azaneyl)ethyl)-N1,N2-dimethylethane-1,2-diamine bromide, represented by the following formula (B-3), was synthesized as follows. In a 100 mL three-necked round-bottom flask equipped with a Liebig compost and dropping funnel, 6.91 g (30 mmol) of hexamethyltriethylenetetramine and 28.7 g of acetonitrile were heated at 83°C. 9.16 g (30 mmol) of bromohexadecane was added dropwise from the dropping funnel over 2 hours, and the mixture was heated and stirred for 3 hours. After the reaction was complete, the mixture was left overnight to allow the dionium salt to precipitate. The mixture was filtered through a Buchner funnel, and the filtrate was collected. The filtrate was concentrated, and the slurry was washed with 100 mL of cold n-hexane, and the mixture was stirred until a white solid settled. Decantation was performed, and the supernatant was removed. This process was repeated three times, and the white solid was collected. The mixture was concentrated under reduced pressure using an evaporator to obtain 5.85 g of a white viscous solid. This was designated as (B-3). １ H-NMR measurement and １３ The chemical shift values ​​in the C-NMR measurements are as follows: 1 H NMR (400MHz, CDCl3) δ; 3.83 (N + CH2, br, 2H), 3.67 (CH2, br, 2H), 3.46 (CH3, s, 6H), 2.78 (CH2, br, 2H), 2.51-2.21 (CH2, m, 26H), 1.76 (CH2, br, 2H), 1.36-1.25 (CH2, br, 26H), 0.88 (CH3, t, 3H). 13C NMR (100MHz, CDCl3) δ; 65.1, 60.4, 57.4, 57.2, 55.9, 55.8, 55.6, 52.1, 51.6, 46.0, 45.9, 42.6, 31.9, 29.8, 29.7, 29.6, 29.5, 29.4, 29.3, 26.4, 22.9, 22.7, 14.2

[0130] 4.2.4. Synthesis Example 4 2-(Hexadecyldimethyl-14-azaneyl)-N,N-dimethylethan-1-amine bromide, represented by the following formula (B-4), was synthesized as follows. 5.81 g (50 mmol) of tetramethyldiethyleneamine and 63.2 g of acetonitrile were added to a 200 mL three-necked flask equipped with a Limebloh funnel, and the mixture was heated and stirred at 83°C. 15.27 g (50 mmol) of bromohexadecane was added dropwise over 2 hours using a dropping funnel, and the mixture was stirred for 3 hours. After the reaction was complete, the mixture was left overnight to allow the dionium salt to precipitate. The mixture was filtered through a Buchner funnel, and the filtrate was collected. The filtrate was concentrated, the slurry was washed with 100 mL of cold n-hexane, and 10 g was collected using a Buchner funnel. The white solid was dried under reduced pressure at room temperature. This was designated as (B-4). １ H-NMR measurement and １３ The chemical shift values ​​in the C-NMR measurements are as follows: 1 H NMR (400MHz, CDCl3) δ; 3.83 (N + CH2, br, 2H), 3.67 (CH2, br, 2H), 3.46 (CH3, s, 6H), 2.76 (CH2, br, 2H), 2.30 (CH3, s, 6H), 1.73 (CH2, br, 2H), 1.35-1.25 (CH2, br, 26H), 0.88 (CH3, t, 3H). 13 C NMR (100MHz, CDCl3) δ; 64.9, 60.3, 54.1, 51.6, 45.5, 32.0, 29.8, 29.7, 29.5, 29.4, 29.3, 26.4, 23.0, 22.8, 14.2

[0131] 4.2.5. Synthesis Example 5 N1-(2-(Dodecyldimethyl-14-azaneyl)ethyl)-N1,N2,N2-trimethylethane-1,2-diamine bromide, represented by the following formula (B-5), was synthesized as follows. 5.07 g (22 mmol) of hexamethyltetramine and 29.2 g of acetonitrile were placed in a 100 mL three-necked flask equipped with a Liebig condenser and a dropping funnel, and stirred. 4.66 g (18.7 mmol, 0.85 equivalents) of bromododecane was added dropwise from the dropping funnel, and the mixture was heated and stirred at 80°C for 6 hours. After the reaction was complete, the mixture was concentrated under reduced pressure using an evaporator, and a viscous solid was confirmed. 40 g of n-hexane / methylene chloride = 15 / 1 (vol%) was added to dissolve any unreacted substances. This procedure was repeated three times, and the solution was removed as waste liquid. The viscous solid changed from yellow to white. The mixture was concentrated again under reduced pressure using an evaporator, yielding 3.79 g of a foamy white waxy solid. The white waxy solid was dried under reduced pressure at room temperature. This was designated (B-5). １ H-NMR measurement and １３ The chemical shift values ​​in the C-NMR measurements are as follows: 1 H NMR (400MHz, CDCl3) δ; 3.83 (N + CH2, br, 2H), 3.67 (CH2, br, 2H), 3.46 (CH3, s, 6H), 2.82 (CH2, br, 2H), 2.51-2.21 (CH2, m, 22H), 1.76 (CH2, br, 2H), 1.36-1.25 (CH2, br, 18H), 0.88 (CH3, t, 3H). 13 C NMR (100MHz, CDCl3) δ; 65.1, 60.4, 57.4, 57.2, 56.2, 56.0, 55.9, 51.5, 46.0, 45.9, 43.0, 42.5, 31.9, 29.6, 29.5, 29.4, 29.3, 26.4, 22.9, 22.7, 14.2

[0132] 4.2.6. Synthesis Example 6 N-(2-((2-((2-(Dodecyldimethyl-14-azaneyl)ethyl)(methyl)amino)ethyl)(methyl)amino)ethyl)-N,N-dimethyldodecan-1-aminium dibromide, represented by the following formula (B-6), was synthesized as follows. In a 100 mL three-necked flask equipped with a Liebig condenser, 4.61 g (20 mmol) of hexamethyltetramine, 9.97 g (40 mmol) of bromododecane, and 29.2 g of acetonitrile were added using a dropping funnel. The mixture was heated and stirred at 80°C for 6 hours. After the reaction was complete, three liquid-liquid washes were performed with n-hexane / acetonitrile, and the acetonitrile layer was collected and concentrated. 50 g of ethyl acetate was added to precipitate a white solid, and the slurry was washed in solution. 13.1 g of the white solid was collected using a Buchner funnel. The white solid was dried under reduced pressure at room temperature. This was designated as (B-6). １ H-NMR measurement and １３ The chemical shift values ​​in the C-NMR measurements are as follows: 1 H NMR (400MHz, CDCl3) δ; 3.86 (N + CH2, br, 4H), 3.60 (CH2, br, 4H), 3.45 (CH3, s, 12H), 2.97 (CH2, br, 4H), 2.68 (CH2, br, 4H), 2.34 (CH3, s, 6H), 1.76 (CH2, br, 2H), 1.36-1.25 (CH2, br, 36H), 0.88 (CH3, t, 6H).・ 13 C NMR (100MHz, CDCl3) δ; 65.3, 61.2, 54.7, 51.5, 43.1, 31.9, 29.7, 29.5, 29.4, 26.4, 23.0, 22.8, 14.2

[0133] 4.2.7. Synthesis Example 7 N-(2-((2-((2-(Hexadecyldimethyl-14-azaneyl)ethyl)(methyl)amino)ethyl)(methyl)amino)ethyl)-N,N-dimethylhexadecan-1-aminium dibromide, represented by the following formula (B-7), was synthesized as follows. In a 100 mL round-bottom flask equipped with a Limebloch glass, 6.35 g (20.8 mmol) of bromohexadecane, 2.40 g (10.4 mmol) of hexamethyltriethylenetetramine, and 26 g of acetonitrile were added and heated and stirred at 83°C for 6 hours. After the reaction was complete, liquid-liquid washing was performed three times with n-hexane / acetonitrile, and the acetonitrile layer was collected and concentrated. A white solid was obtained, which was washed with ethyl acetate, and 8.1 g was collected using a Buchner funnel. The white solid was dried under reduced pressure at room temperature. This was designated as (B-7). １ H-NMR measurement and １３ The chemical shift values ​​in the C-NMR measurements are as follows: 1 H NMR (400MHz, CDCl3) δ; 3.86 (N + CH2, br, 4H), 3.60 (CH2, br, 4H), 3.45 (CH3, s, 12H), 2.97 (CH2, br, 4H), 2.68 (CH3, s, 4H), 2.34 (CH3, s, 6H), 1.76 (CH2, br, 4H), 1.36-1.25 (CH2, br, 54H), 0.88 (CH3, t, 6H).・ 13 C NMR (100MHz, CDCl3) δ; 65.3, 61.2, 54.7, 51.5, 43.1, 32.0, 29.7, 29.6, 29.5, 29.4, 29.3, 26.4, 23.0, 22.8, 14.2

[0134] 4.2.8. Synthesis Example 8 N1,N1'-(Ethane-1,2-diyl)bis(N2-dodecyl-N1,N2,N2-trimethyl-N1-propylethane-1,2-diaminium) tetra bromide, represented by the following formula (B-8), was synthesized as follows. In a 100 mL round-bottom flask equipped with a condenser bottle, 4.37 g (6 mmol) of N-(2-((2-((2-(dodecyldimethyl-14-azaneyl)ethyl)(methyl)amino)ethyl)(methyl)amino)ethyl)-N,N-dimethyldodecan-1-aminium, 1.48 g (6 mmol) of propyl bromide, and 18 g of acetonitrile were added, and the mixture was heated and stirred at 83°C for 6 hours. After the reaction was complete, the mixture was washed three times with n-hexane (50 g) / acetonitrile (30 g), and the acetonitrile layer was collected and concentrated. This was designated as (B-8). １ H-NMR measurement and １３ The chemical shift values ​​in the C-NMR measurements are as follows: 1 H NMR (400MHz, CDCl3) δ; 3.86 (N + CH2, br, 4H), 3.60 (CH2, br, 4H), 3.45 (CH3, s, 12H), 2.97 (CH2, br, 8H), 2.68 (CH2, br, 4H), 2.34 (CH3, s, 6H), 1.76 (CH2, br, 2H), 1.36-1.25 (CH2, br, 40H), 0.88-0.86 (CH3, t, 12H). 13 C NMR (100MHz, CDCl3) δ; 65.3, 62.7, 62.3, 61.2, 54.7, 51.5, 43.1, 31.9, 29.7, 29.5, 29.4, 26.4, 23.0, 22.8, 21.4, 18.9, 14.2

[0135] 4.2.9. Measurement of Total Amine Value The total amine value of component (B) was calculated based on the product standard test method described in Kao Farmin. 0.2 g of component (B) was weighed and dissolved in 10 g of ethanol, and one drop of 2% bromophenol blue (manufactured by Wako Pure Chemical Industries, Ltd.) ethanol solution was added to make a blue solution. Titration was then performed using a burette with 0.1 N hydrochloric acid solution (manufactured by Wako Pure Chemical Industries, Ltd.), and the endpoint was reached when the solution turned green, and the titration volume of 0.1 N hydrochloric acid solution was read. Based on the titration volume, the total amine value was calculated using the following formula. The results are shown in Tables 1 and 2 below. <Total Amine Value> (A １ (Titration volume mL) × N normal of HCl ethanol solution × 56.108 (KOH molecular weight)) / S (Sample volume g)

[0136] 4.3. Preparation of Chemical Mechanical Polishing Compositions The components were mixed to obtain the compositions shown in Tables 1 and 2 below. Nitric acid (manufactured by Kanto Chemical Co., Ltd., trade name "Nitric Acid 1.38") or potassium hydroxide aqueous solution (manufactured by Kanto Chemical Co., Ltd., trade name "48% Potassium Hydroxide Aqueous Solution") was added to adjust the pH to the pH shown in Tables 1 and 2 below. Pure water was then added so that the total amount of all components was 100 parts by mass, thereby preparing the chemical mechanical polishing compositions for each example and comparative example.

[0137] 4.4. Evaluation Method 4.4.1. Polishing Speed ​​Evaluation Using the chemical mechanical polishing composition prepared above, a 12-inch diameter wafer with a 5000 Å molybdenum film was used as the workpiece for a chemical mechanical polishing test under the following conditions. (Polishing conditions) ・Polishing equipment: Applied Materials, Inc., model "Reflexion-LK" ・Polishing pad: Fuji Spinning Co., Ltd., "Porous polyurethane pad; H800-type1 (3-1S) 775" ・Chemical mechanical polishing composition supply rate: 300 mL / min ・Plate rotation speed: 93 rpm ・Head rotation speed: 90 rpm ・Head pressing pressure: 2.0 psi ・Polishing time: 60 seconds ・Polishing speed (Å / min) = (Thickness of film before polishing (Å) - Thickness of film after polishing (Å)) / Polishing time (min)

[0138] The thickness of the molybdenum film was calculated by measuring the resistance using a DC four-probe method with a resistivity meter (KLA-Tencor, model "RS-100"), and then using the following formula based on this sheet resistance value and the volume resistivity of molybdenum: Film thickness (Å) = (Volume resistivity of molybdenum film (Ω・m) ÷ Sheet resistance value (Ω)) × 10 １０

[0139] The evaluation criteria for the polishing speed of the molybdenum film are as follows. The evaluation results for the polishing speed of the molybdenum film are shown in Tables 1 and 2 below. (Evaluation Criteria) A: If the polishing speed is 150 Å / min or more, it is judged to be very good. B: If the polishing speed is 100 Å / min or more and less than 150 Å / min, it is judged to be good. C: If the polishing speed is less than 100 Å / min, it is judged to be unsuitable for practical use and is therefore unsatisfactory.

[0140] 4.4.2. Etching Rate Evaluation The chemical mechanical polishing composition prepared above was heated to 60°C, and a wafer piece with a 200 nm molybdenum film, cut to 30 mm x 10 mm, was immersed in the mixture for 10 minutes. After that, the wafer piece was removed and washed with running water, and the thickness of the molybdenum film was measured using the same method as in "4.4.1. Polishing Rate Evaluation" above. The etching rate was then calculated from the change in the thickness of the molybdenum film before and after immersion using the following formula: Etching rate of molybdenum film (Å / min) = (Thickness of molybdenum film before etching (Å) - Thickness of molybdenum film after etching (Å)) / Etching time (min)

[0141] The evaluation criteria for the etching rate of molybdenum films are as follows. The evaluation results for the etching rate of molybdenum films are shown in Tables 1 and 2 below. (Evaluation Criteria) A: If the etching rate is less than 1 Å / min, it is judged to be very good. B: If the etching rate is 1 Å / min or more and less than 4 Å / min, it is judged to be good. C: If the etching rate is 4 Å / min or more, it is judged to be unsuitable for practical use and is deemed unsatisfactory.

[0142] 4.4.3. Stability Evaluation Generally, after polishing using a chemical mechanical polishing composition containing abrasive grains, the polished surface is cleaned with a cleaning agent. This cleaning agent contains water-soluble polymers such as polyacrylic acid to enhance the abrasive grain removal effect. As a result, when the chemical mechanical polishing composition remaining on the polished surface mixes with the water-soluble polymer during the cleaning process, abrasive grains may aggregate and generate coarse particles, or the water-soluble polymer may precipitate and remain on the polished surface when mixed with the chemical mechanical polishing composition. Therefore, even if cleaning is performed after the polishing process, a clean polished surface cannot be obtained, which can lead to poor yield in semiconductor manufacturing and make the product unsuitable for practical use. To evaluate the generation of foreign matter resulting from the mixing of the cleaning agent and the chemical mechanical polishing composition during such a cleaning process, the following model evaluation was performed.

[0143] A test composition was prepared by adding polyacrylic acid (manufactured by Toagosei Co., Ltd., product name: Aron A-30SL, Mw3000) to the chemical mechanical polishing composition prepared above to a concentration of 0.01%. After storing this test composition in a constant temperature storage chamber at 20°C for one day, the test composition was evaluated using a particle size distribution analyzer (manufactured by Malvern, model "Zetasizer Ultra"), and the average secondary particle diameter based on scattered light intensity of the particles contained in the test composition was measured. The particle size change rate was calculated using the following formula: Particle size change rate (%) = (Average secondary particle diameter (Å) obtained by measuring the test composition after storing it in a constant temperature storage chamber at 20°C for one day) / (Average secondary particle diameter (Å) obtained by measuring the chemical mechanical polishing composition) × 100

[0144] The stability evaluation criteria are as follows. The evaluation results are shown in Tables 1 and 2 below. (Evaluation Criteria) A: If the particle size change rate is 95% or more and 105% or less, no foreign matter is generated and it is judged to be very good. B: If the particle size change rate is more than 105% and 150% or less, the generation of foreign matter is very low and it is judged to be good as it can be used in practice. C: If the particle size change rate is more than 150%, or if sedimentation is confirmed by visual inspection, the generation of foreign matter such as coarse particles is observed and it is judged to be poor as it is difficult to use in practice.

[0145] 4.5. Evaluation Results Tables 1 and 2 below show the composition of the chemical mechanical polishing composition used in each example and comparative example, as well as the evaluation results.

[0146]

[0147]

[0148] The following products or reagents were used for each component in Tables 1 and 2 above. <(B) Component> ・B-9: Manufactured by Sanyo Chemical Industries, Ltd., product name "Revon S", N-(2-{[2-(dodecylamino)ethyl]amino}ethyl)glycine ・B-10: Manufactured by NOF Corporation, product name "Nissanamine DOB-R", 1-oleylpropanediamine <(C) Component> ・Iron nitrate nonahydrate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name "Iron(III) nitrate nonahydrate" <(D) Component> ・Hydrogen peroxide: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 30% aqueous solution <(E) Component> ・EDTA: Manufactured by Tokyo Chemical Industries, Ltd., ethylenediaminetetraacetic acid, product name "Ethylenediaminetetraacetic acid"

[0149] The chemical mechanical polishing compositions of Examples 1 to 15 demonstrate that the polishing speed of the molybdenum film is sufficiently high, enabling high-speed polishing of the molybdenum film. Furthermore, the chemical mechanical polishing compositions of Examples 1 to 15 demonstrate that component (B) adsorbs onto the surface of the molybdenum film, effectively suppressing etching of the molybdenum surface.

[0150] In contrast, the chemical mechanical polishing compositions of Comparative Examples 1 and 2 do not contain a component equivalent to component (B), and therefore, etching of the molybdenum surface is not suppressed. Furthermore, it can be seen that the stability of components (B-9) and (B-10) is compromised because their total amine values ​​are too high.

[0151] The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes configurations that are substantially identical to the configurations described in the embodiments (for example, configurations with the same function, method and result, or configurations with the same purpose and effect). The present invention also includes configurations in which non-essential parts of the configurations described in the embodiments are replaced. Furthermore, the present invention includes configurations that produce the same effects or achieve the same purpose as the configurations described in the embodiments. Furthermore, the present invention includes configurations that add known technology to the configurations described in the embodiments.

[0152] 10...Substrate, 12...Silicon oxide film, 14...Contact hole, 16...Molybdenum film, 42...Slurry supply nozzle, 44...Slurry (composition for chemical mechanical polishing), 46...Polishing pad, 48...Turntable, 50...Semiconductor substrate, 52...Carrier head, 54...Water supply nozzle, 56...Dresser, 100...Workpiece, 200...Chemical mechanical polishing apparatus

Claims

1. A chemical mechanical polishing composition comprising: (A) abrasive grains; (B) a compound having a partial structure represented by the following formula (1) in one molecule; and (F) a liquid medium, wherein the pH is 1 or more and 5 or less. (In formula (1), R １ and R ２ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R ３ represents an alkyl group having 8 to 20 carbon atoms. X － represents at least one selected from the group consisting of alkyl sulfonate, fluorosulfonate, toluene sulfonate, styrene sulfonate, alkyl sulfonimide, trifluoromethane sulfonimide, Br － , Cl － , SCN － , PF ６ － , BF ４ － and trifluoroacetate. * represents a binding site.) 2. The chemical mechanical polishing composition according to claim 1, wherein component (B) is a compound having a substructure represented by formula (1) and a tertiary amine structure in one molecule.

3. The chemical mechanical polishing composition according to claim 1, further comprising at least one selected from the group consisting of (C) iron(III) compounds and (D) oxidizing agents.

4. The chemical mechanical polishing composition according to claim 1, further comprising (C) an iron(III) compound and (E) a compound having 1 to 3 of at least one functional group selected from the group consisting of an amino group and a salt thereof.

5. The chemical mechanical polishing composition according to claim 4, wherein the total amine value of component (E) is 0 to 320 mg KOH / g.

6. The chemical mechanical polishing composition according to claim 1, wherein the average secondary particle diameter of component (A) is 10 nm to 120 nm.

7. The chemical mechanical polishing composition according to claim 1, wherein the content of component (A) is 0.1% to 5% by mass when the total mass of the chemical mechanical polishing composition is 100% by mass.

8. The chemical mechanical polishing composition according to claim 1, used for polishing a surface to be polished having at least one of a molybdenum film and a tungsten film.

9. A polishing method comprising the step of polishing a surface to be polished having at least one of a molybdenum film and a tungsten film using a chemical mechanical polishing composition according to any one of claims 1 to 8.

10. The compound represented by the following formula (2). (In formula (2), R ４ X represents an alkyl group with 12 to 20 carbon atoms. － These include alkyl sulfonates, fluorosulfonates, toluene sulfonates, styrene sulfonates, alkyl sulfonimides, trifluoromethanesulfonimides, and Br. － , Cl － SCN － , PF ６ － BF ４ － (This represents at least one selected from the group consisting of trifluoroacetates.)

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