Chemical mechanical polishing composition, rinsing composition, chemical mechanical polishing method for a substrate, and rinsing method for a substrate.

Abstract

To provide: a novel chemical mechanical polishing composition and rinse composition which contain useful additive components useful for achieving at least one of reduction of protruding parts on the periphery of a hard laser mark and reduction of haze; and a chemical mechanical polishing method and rinsing method using these.SOLUTION: Provided are: a chemical mechanical polishing composition comprising a polishing agent, a basic component, at least one compound selected from the group consisting of quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having amide structures, and an aqueous carrier; a rinse composition comprising at least one of the above compounds and an aqueous carrier; and a chemical mechanical polishing method and rinsing method of a substrate using these.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to chemical mechanical polishing compositions and rinsing compositions, as well as chemical mechanical polishing methods and rinsing methods for substrates using the same. [Background technology]

[0002] Substrates such as silicon wafers used in the manufacture of semiconductor devices require extremely high surface quality, and chemical mechanical polishing (CMP) technology has traditionally been used to ensure such surface quality. Generally, CMP of substrates such as silicon wafers consists of multiple steps, including, for example, a preliminary polishing step and a finish polishing step.

[0003] In the preliminary polishing process, the surface of the substrate is polished using a polishing slurry with relatively strong abrasive power, thereby efficiently adjusting the shape and surface condition of the substrate. On the other hand, in the finish polishing process, a polishing slurry with generally weaker abrasive power than that used in the preliminary polishing process is used to improve the surface quality of the substrate after the preliminary polishing process.

[0004] On substrates such as silicon wafers, marks such as barcodes, numbers, and symbols (hard laser marks) are sometimes applied to the surface by irradiating them with laser light for identification purposes. Due to the energy of the laser light, the edges of the hard laser marks undergo alteration such as polysiliconization, causing them to harden. As a result, in the preliminary polishing process, conventional polishing compositions may cause raised areas around the hard laser marks. Such raised areas around the hard laser marks can reduce the flatness of the substrate and may significantly affect the yield of semiconductor production.

[0005] Patent Document 1 describes a polishing composition for use in polishing silicon wafers, comprising silica particles, a weak acid salt, and a quaternary ammonium compound, wherein the BET average particle diameter of the silica particles is 50 nm or less, and the content Y [mol / L] of the quaternary ammonium compound in the polishing composition satisfies formula (1) 0.80 ≤ (Y / Y0) (where Y0 [mol / L] is an amount defined by formula (2) Y0 = AX + B, based on the theoretical buffer ratio A between the quaternary ammonium compound and the weak acid salt, the content X [mol / L] of the weak acid salt in the polishing composition, and the amount B [mol / L] of the quaternary ammonium compound contained in the polishing composition that is adsorbed on the silica particles). Furthermore, Patent Document 1 states that, according to the above polishing composition, by effectively utilizing the buffering effect between the quaternary ammonium compound and the weak acid salt, pH fluctuations of the polishing composition during polishing can be suitably suppressed, and good polishing efficiency can be maintained, thereby efficiently eliminating the raised edges around hard laser marks.

[0006] Furthermore, in CMP of substrates such as silicon wafers, the increasing demand in recent years, along with the improved performance and integration of semiconductor devices, has led to an increasingly strong demand for improved surface quality in addition to increased productivity. In particular, the miniaturization of semiconductor device design rules is progressing year by year in order to achieve high integration and high speed in large-scale integrated circuits (ULSI) used in computers. Consequently, the importance of managing nano-level surface defects, which were not previously considered a problem, is increasing.

[0007] Surface defect inspection equipment is generally used to manage surface defects in substrates such as silicon wafers. The defects detected by such surface defect inspection equipment include foreign matter and residues on the substrate that could not be completely removed during the polishing process and subsequent rinsing process. As an example of such surface defect inspection equipment, it is generally known that irradiates the substrate surface with light, such as laser light, and detects defects present on the substrate surface by detecting the reflected or scattered light generated on the substrate surface.

[0008] On the one hand, when such strong light is irradiated on the substrate surface, cloudiness may be observed due to irregular reflection caused by the roughness of the substrate surface. This cloudiness is called haze, and since haze is closely related to the surface roughness of the substrate, it can be used as a measure of the surface roughness. In recent years, with the rapid progress of surface defect inspection devices, although surface defects can be observed up to the nanometer level, if there is haze on the substrate surface, the irregular reflection light generated by the haze may become background noise and interfere with defect detection by the surface defect inspection device. Therefore, as the size of the surface defects to be managed becomes smaller, the need to appropriately achieve a lower surface roughness in polishing processes such as the preliminary polishing process and the finish polishing process to reduce the haze level is increasing.

[0009] In Patent Document 2, there is a method for polishing a silicon substrate, which includes a preliminary polishing step of preliminarily polishing the silicon substrate. In this preliminary polishing step, a first polishing slurry and a second polishing slurry are supplied to the silicon substrate to be polished by switching them in this order during the polishing of the silicon substrate. Here, as the second polishing slurry, it contains abrasive grains A2, and the volume average diameter (M v , BET ) of the abrasive grains A2 is smaller than the volume average diameter (M v ) of the abrasive grains A1 contained in the first polishing slurry, and the ratio (M BET ) of M v of the abrasive grains A2 to the BET diameter (D v ) of the abrasive grains A2 is less than or equal to the ratio (M BET ) of M BET of the abrasive grains A1 to the BET diameter (D v ) of the abrasive grains A1 (M v / D BET ). A polishing method using such a slurry is described. Also, in Patent Document 2, according to the preliminary polishing step of switching and supplying a first polishing slurry containing abrasive grains A1 and a second polishing slurry containing abrasive grains A2 whose M v is smaller and M v / D BET is equal to or less than that of the abrasive grains A1 during polishing, it is described that the elimination of the ridge at the periphery of the hard laser mark and the reduction of the surface roughness can be preferably achieved simultaneously. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Publication No. 2015-233031 [Patent Document 2] Japanese Patent Publication No. 2017-183359 [Overview of the Initiative] [Problems that the invention aims to solve]

[0011] As described above, Patent Document 1 teaches the use of quaternary ammonium compounds as additives that can eliminate the raised edges around hard laser marks. However, Patent Document 1 only specifically discloses tetramethylammonium hydroxide (TMAH) as the quaternary ammonium compound, and does not adequately investigate whether other quaternary ammonium compounds can eliminate the raised edges around hard laser marks. Furthermore, Patent Document 1 does not investigate the effect of quaternary ammonium compounds on reducing surface roughness or haze.

[0012] As described above, Patent Document 2 investigates how to achieve both the elimination of raised edges around hard laser marks and the reduction of surface roughness by using two different types of abrasive grains in the pre-polishing process, in terms of parameters defined by the volume-average diameter and BET diameter. However, no sufficient investigation has been conducted into additive components that can achieve the elimination of raised edges around hard laser marks, the reduction of surface roughness, and ultimately the reduction of haze.

[0013] As mentioned earlier, the proper removal of raised areas around hard laser marks caused by hard laser marking is extremely important from the standpoint of improving the flatness of the substrate and, consequently, improving the yield in semiconductor production. Furthermore, with the recent increase in performance and integration of semiconductor devices, there is a growing need to achieve lower surface roughness on substrates such as silicon wafers to reduce haze levels. Therefore, in the field of technology, there is a demand for additive components that can effectively reduce raised areas around hard laser marks and / or reduce haze in polishing compositions used in polishing processes such as pre-polishing and finish polishing processes, as well as in rinsing processes after polishing. There is a need for polishing compositions and rinsing compositions containing such additive components.

[0014] Therefore, the present invention aims to provide novel chemical mechanical polishing compositions and rinsing compositions containing additive components useful for achieving at least one of the reduction of raised portions around hard laser marks and the reduction of haze, as well as chemical mechanical polishing methods and rinsing methods for substrates using the same. [Means for solving the problem]

[0015] The present invention, which achieves the above objective, is as follows. (1) Abrasives, Basic components, At least one compound selected from the group consisting of quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure, and Water-based carrier A chemical mechanical polishing composition containing the following: (2) The chemical mechanical polishing composition according to (1) above, wherein the at least one compound comprises two or more selected from quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure. (3) The at least one of the compounds comprises a quaternary polyammonium salt, and the quaternary polyammonium salt is of the following general formula (1): [ka] It has, in the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 A is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, A is independently a substituted or unsubstituted linear or branched alkylene group having 1 to 30 carbon atoms, n is an integer from 1 to 10, and X - A chemical mechanical polishing composition according to (1) or (2) above, wherein is a counterion. (4) The chemical mechanical polishing composition according to (3) above, wherein the quaternary polyammonium salt is a quaternary diammonium salt, A in the general formula (1) is a substituted or unsubstituted linear or branched alkylene group having 1 to 15 carbon atoms, and n is 1. (5) The above-mentioned compound comprises at least one quaternary ammonium salt having 6 or more carbon atoms, and the above-mentioned quaternary ammonium salt having 6 or more carbon atoms is of the following general formula (2): [ka] It has, in the formula, R 7 , R 8 and R 9 R is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms or a benzyl group, 10 is a substituted or unsubstituted linear or branched alkyl group having 2 to 30 carbon atoms, Y - A chemical mechanical polishing composition according to (1) or (2) above, wherein is a counterion. (6) The chemical mechanical polishing composition according to (1) or (2) above, wherein at least one compound comprises an alkylated polymer having an amide structure, and the alkylated polymer having an amide structure is alkylated polyvinylpyrrolidone. (7) A chemical mechanical polishing composition according to any one of (1) to (6) above, further comprising tetramethylammonium hydroxide. (8) The chemical mechanical polishing composition according to any one of (1) to (7) above, further comprising a water-soluble polymer different from the alkylated polymer having the amide structure. (9) The chemical mechanical polishing composition according to (8) above, wherein the water-soluble polymer comprises at least one selected from the group consisting of polyvinylpyrrolidone, polyvinylacetamide, cellulose derivatives, and polymers containing polyvinyl alcohol structural units. (10) At least one compound selected from the group consisting of quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure, and Water-based carrier A rinse composition containing [the specified ingredient]. (11) The rinse composition according to (10) above, wherein the at least one compound comprises two or more selected from quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure. (12) The at least one of the compounds comprises a quaternary polyammonium salt, wherein the quaternary polyammonium salt is of the following general formula (1): [ka] It has, in the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 A is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, A is independently a substituted or unsubstituted linear or branched alkylene group having 1 to 30 carbon atoms, n is an integer from 1 to 10, and X - The rinse composition according to (10) or (11) above, wherein is a counterion. (13) The rinse composition according to (12) above, wherein the quaternary polyammonium salt is a quaternary diammonium salt, A in the general formula (1) is a substituted or unsubstituted linear or branched alkylene group having 1 to 15 carbon atoms, and n is 1. (14) The above-mentioned compound comprises at least one quaternary ammonium salt having 6 or more carbon atoms, and the above-mentioned quaternary ammonium salt having 6 or more carbon atoms is of the following general formula (2): [ka] It has, in the formula, R 7 , R 8 and R 9 R is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms or a benzyl group, 10 is a substituted or unsubstituted linear or branched alkyl group having 2 to 30 carbon atoms, Y - The rinse composition according to (10) or (11) above, wherein is a counterion. (15) The rinse composition according to (10) or (11), wherein the at least one compound comprises an alkylated polymer having an amide structure, and the alkylated polymer having an amide structure is alkylated polyvinylpyrrolidone. (16) The rinse composition according to any one of (10) to (15) above, further comprising tetramethylammonium hydroxide. (17) The rinse composition according to any one of (10) to (16) above, further comprising a water-soluble polymer different from the alkylated polymer having the amide structure. (18) The rinse composition according to (17) above, wherein the water-soluble polymer comprises at least one selected from the group consisting of polyvinylpyrrolidone, polyvinylacetamide, cellulose derivatives, and polymers containing polyvinyl alcohol structural units. (19) A step of bringing the substrate into contact with the polishing pad and the chemical mechanical polishing composition described in any one of the above items (1) to (9). The process of moving the polishing pad with respect to the substrate and the chemical mechanical polishing composition between them, and A step of polishing the substrate by wearing down at least a portion of it. A chemical mechanical polishing method for a substrate, including the method described above. (20) A step of bringing the substrate after chemical mechanical polishing into contact with a polishing pad and the rinse composition described in any one of the above items (10) to (18), and The process of moving the polishing pad with the rinse composition between the substrate and the substrate. A method for rinsing a substrate, including [the specified element]. (21) A method for chemical mechanical polishing of a substrate using a polishing apparatus comprising an upper platen and a lower platen to which polishing pads are attached, and a carrier plate having at least one holding hole for holding the substrate, The process involves holding the substrate in at least one holding hole of the carrier plate, and then sandwiching the carrier plate between the upper and lower plates to which polishing pads are attached, respectively, and A process in which the carrier plate is rotated and revolved while supplying the chemical mechanical polishing composition described in any one of items (1) to (9) above to the polishing surface of the substrate, thereby simultaneously polishing both sides of the substrate. A chemical mechanical polishing method for a substrate, including the method described above. (22) A method for rinsing a substrate using a polishing apparatus comprising an upper platen and a lower platen to which polishing pads are attached, and a carrier plate having at least one holding hole for holding the substrate, A step of rotating and revolving the carrier plate while supplying the rinse composition described in any one of items (10) to (18) above to the polished surface of the substrate after chemical mechanical polishing. A method for rinsing a substrate, including [the specified element]. [Effects of the Invention]

[0016] According to the present invention, by using at least one compound selected from the group consisting of quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure as an additive component, it is possible to reduce the raised portion around hard laser marks, particularly in pre-polishing, and / or reduce haze on the substrate surface in both pre-polishing and finish polishing, compared to cases where the at least one compound is not used. Therefore, the chemical mechanical polishing composition of the present invention containing such an additive component can improve the flatness of the substrate by reducing the raised portion around hard laser marks, and consequently improve the yield in semiconductor production. Alternatively or in addition, the chemical mechanical polishing composition of the present invention containing such an additive component can reduce background noise during defect detection by a surface defect inspection device by reducing haze on the substrate surface, thereby facilitating the detection and management of minute surface defects, such as nano-level surface defects, using the surface defect inspection device. In addition, the chemical mechanical polishing composition of the present invention can also be effectively used in polishing substrates such as low-resistivity silicon wafers. [Modes for carrying out the invention]

[0017] <Chemical mechanical polishing composition> The chemical mechanical polishing composition of the present invention is Abrasives, Basic components, At least one compound selected from the group consisting of quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure, and Water-based carrier It is characterized by containing [something].

[0018] As mentioned earlier, in relation to hard laser marks (hereinafter also referred to as "HLM"), which are applied to the surface of substrates such as silicon wafers by irradiating them with laser light for purposes such as identification, it is known that raised areas occur on the substrate surface around the HLMs during the pre-polishing process. Appropriately removing such raised areas is extremely important from the standpoint of improving the flatness of the substrate and, consequently, improving the yield in semiconductor production. Furthermore, with the recent increase in performance and integration of semiconductor devices, the importance of managing nano-level surface defects, which were not previously considered a problem, has increased. In connection with this, there is a growing need to achieve lower surface roughness for substrates such as silicon wafers and reduce the haze level.

[0019] Therefore, the inventors investigated additive components in chemical mechanical polishing compositions and rinse compositions that are useful for achieving at least one, preferably both, of the reduction of raised portions around the HLM periphery caused by the application of HLM and the reduction of haze on the substrate surface. As a result, the inventors found that by using at least one compound selected from the group consisting of quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure as such additive components, it is possible to reduce the raised portions around the HLM periphery, particularly in pre-polishing, and / or reduce haze on the substrate surface in both pre-polishing and finish polishing, compared to cases where the at least one compound is not used. In addition, the inventors found that when the above at least one compound is used, even with substrates such as low-resistivity silicon wafers, which are generally known to be difficult to chemical mechanically polish, the polishing speed can be improved, and haze and surface defects can be reduced, compared to cases where the at least one compound is not used.

[0020] Therefore, according to the chemical mechanical polishing composition of the present invention containing such additive components, it is possible to improve the flatness of the substrate by reducing the raised portion around the HLM periphery, and consequently improve the yield in semiconductor production. Alternatively or in addition, according to the chemical mechanical polishing composition of the present invention containing such additive components, it is possible to reduce background noise during defect detection by a surface defect inspection device by reducing haze on the substrate surface, thereby facilitating the detection and management of minute surface defects, such as nano-level surface defects, using the surface defect inspection device. Furthermore, according to the present invention, the above-mentioned additive components can achieve the same effect not only when used in the chemical mechanical polishing composition but also when used in the rinse composition. In addition, the chemical mechanical polishing composition of the present invention can be effectively used in polishing substrates such as low-resistivity silicon wafers.

[0021] [Abrasives] The abrasive in the present invention may be any suitable abrasive known to those skilled in the art in the chemical mechanical polishing of semiconductor substrates such as silicon wafers. While not particularly limited, the abrasive may be selected from the group consisting of, for example, alumina (e.g., α-alumina, γ-alumina, δ-alumina, and fumed alumina), silica (e.g., colloidal silica, precipitated silica, fumed silica), ceria, titania, zirconia, germania, magnesia, co-formed products thereof, and any combination thereof. Preferably, the abrasive is selected from the group consisting of alumina, silica, ceria, zirconia, and combinations thereof, more preferably silica, particularly colloidal silica or ceria, and most preferably colloidal silica.

[0022] In the present invention, the abrasive can have any suitable particle size. While not particularly limited, for example, the abrasive can have an average primary particle size of 0.01 μm or more, 0.015 μm or more, 0.02 μm or more, or 0.025 μm or more, and an average primary particle size of 3 μm or less, 1.5 μm or less, 0.8 μm or less, 0.5 μm or less, or 0.1 μm or less. From the viewpoint of improving the polishing speed of the substrate, the abrasive preferably has an average primary particle size of 0.01 to 1.5 μm, more preferably 0.01 to 0.5 μm, and most preferably 0.01 to 0.1 μm. Furthermore, if the primary particles aggregate to form secondary particles, from the viewpoint of improving the polishing speed and reducing the surface roughness of the substrate being polished, the abrasive preferably has an average secondary particle size of 0.02 to 3 μm, more preferably 0.02 to 1.0 μm, and most preferably 0.02 to 0.2 μm. The average primary particle size of the abrasive can be determined by observing it with a scanning electron microscope (SEM) or transmission electron microscope (TEM) and performing image analysis. The average secondary particle size can be measured as the volume-averaged particle size using dynamic light scattering.

[0023] The abrasive may be present in the chemical mechanical polishing composition in an amount of, for example, 0.01% by mass or more, 0.02% by mass or more, 0.05% by mass or more, 0.1% by mass or more, or 0.5% by mass or more, based on the total mass of the aqueous carrier and all components dissolved or suspended therein, and in an amount of 50% by mass or less, 20% by mass or less, 15% by mass or less, 12% by mass or less, or 10% by mass or less. The abrasive may be present in the chemical mechanical polishing composition in an amount of preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, and most preferably 0.1 to 10% by mass.

[0024] [Basic components] The basic component in the present invention may be any component that can chemically act on the surface of a semiconductor substrate such as a silicon wafer to assist in mechanical polishing by an abrasive. While not particularly limited, the basic component may be a compound selected from the group consisting of, for example, ammonia, potassium hydroxide, sodium hydroxide, ammonium carbonate, potassium carbonate, sodium carbonate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-(β-aminoethyl)ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, anhydrous piperazine, piperazine hexahydrate, 1-(2-aminoethyl)piperazine, N-methylpiperazine, and any combination thereof. Preferably, the basic component is selected from the group consisting of ammonia, potassium hydroxide, sodium hydroxide, ammonium carbonate, potassium carbonate, and sodium carbonate. More preferably, the basic component is ammonia, potassium hydroxide, or sodium hydroxide, and most preferably potassium hydroxide.

[0025] The basic component may be present in the chemical mechanical polishing composition in an amount of, for example, 0.001% by mass or more, 0.002% by mass or more, 0.005% by mass or more, 0.01% by mass or more, or 0.1% by mass or more, based on the mass of the aqueous carrier and all components dissolved or suspended therein, and in an amount of 5.0% by mass or less, 3.0% by mass or less, 1.5% by mass or less, 1.2% by mass or less, or 1.0% by mass or less. The basic component may be present in the chemical mechanical polishing composition in an amount of preferably 0.001 to 5.0% by mass, more preferably 0.005 to 1.5% by mass, and most preferably 0.01 to 1.0% by mass.

[0026] [Additional ingredients] The chemical mechanical polishing composition of the present invention comprises at least one compound selected from the group consisting of quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure. This at least one compound may comprise two or more of the quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure. By including at least one or a combination of two or more of these compounds as additives, it is possible to reduce the raised portion of the HLM periphery, particularly in pre-polishing, and / or reduce the haze on the substrate surface in both pre-polishing and finish polishing, compared to cases where these compounds are not included.

[0027] Furthermore, it is generally known that substrates such as low-resistivity silicon wafers with resistivity less than 1 Ω·cm, particularly less than 0.010 Ω·cm or less than 0.002 Ω·cm, are difficult to etch and therefore difficult to chemically and mechanically polish. However, according to the present invention, by using at least one compound selected from the group consisting of quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure, it is possible to improve the polishing speed and reduce haze and surface defects not only for general substrates with resistivity of 1 Ω·cm or more, but also for low-resistivity substrates with resistivity of less than 0.002 Ω·cm. Moreover, according to the present invention, by using the above-mentioned at least one compound, it is possible to achieve a significantly better polishing speed than when using amine compounds such as triethylenetetramine, which are generally known as additives for improving polishing speed, or when increasing the amount of abrasive.

[0028] The content of the above-mentioned at least one compound (or, if the at least one compound is a combination of two or more compounds, the total content thereof) is, for example, 0.001% by mass or more, 0.002% by mass or more, 0.005% by mass or more, 0.01% by mass or more, or 0.1% by mass or more, based on the mass of the aqueous carrier and all components dissolved or suspended therein, and may be 10.0% by mass or less, 5.0% by mass or less, 3.0% by mass or less, 1.0% by mass or less, or 0.5% by mass or less. The above-mentioned at least one compound may preferably be 0.001 to 10.0% by mass, more preferably 0.005 to 5.0% by mass, and most preferably 0.01 to 3.0% by mass.

[0029] [Quaternary polyammonium salts] Quaternary polyammonium salts are not particularly limited, but for example, the following general formula (1): [ka] It may have R 1 , R 2 , R 3 , R 4 , R 5 and R 6 A is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, A is independently a substituted or unsubstituted linear or branched alkylene group having 1 to 30 carbon atoms, n is an integer from 1 to 10, and X - It is a counterion.

[0030] R in general formula (1) 1 , R 2 , R 3 , R 4 , R 5 and R 6For example, these may independently be a substituted or unsubstituted 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, or tert-hexyl group, preferably a substituted or unsubstituted methyl group, ethyl group, or n-propyl group. 1 , R 2 , R 3 , R 4 , R 5 and R 6 R may be substituted with, for example, halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl groups, amino groups, alkylamino groups (e.g., methylamino group, ethylamino group), dialkylamino groups (e.g., dimethylamino group, diethylamino group), or may not be substituted. For example, in a particular embodiment of the present invention, R 1 and R 6 R is a methyl group, an ethyl group, or an n-propyl group, and these groups are optionally substituted with a halogen atom, a hydroxyl group, and / or a dimethylamino group. 2 , R 3 , R 4 and R 5 This is an unsubstituted methyl group.

[0031] In general formula (1), A may be any linear or branched alkylene group having 1 to 30 carbon atoms, and the alkylene group may or may not be substituted with, for example, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, an amino group, a methylamino group, a dimethylamino group, etc. The number of carbon atoms in A can be appropriately determined within the range of 1 to 30, but since quaternary polyammonium salts having a larger cationic moiety are considered effective in reducing the raised portion around the HLM, the number of carbon atoms is preferably an integer between 3 and 30, more preferably between 5 and 30, and most preferably between 10 and 30. For example, in a particular embodiment of the present invention, A is a linear alkylene group having 5 to 20 carbon atoms, and may be substituted with a halogen atom or a hydroxyl group as needed.

[0032] On the other hand, using a quaternary polyammonium salt with a higher degree of polymerization may cause agglomeration of abrasives such as silica contained in the composition. In such cases, the resulting composition may not be usable in chemical mechanical polishing, or its polishing performance may be significantly reduced. Therefore, n in general formula (1) is generally an integer from 1 to 100, preferably from 1 to 50, more preferably from 1 to 10, and most preferably from 1 to 3. In the present invention, the quaternary polyammonium salt can have any suitable molecular weight. Although not particularly limited, the quaternary polyammonium salt generally has an average molecular weight of about 15,000 or less, for example, 7,500 or less or 1,500 or less.

[0033] X in general formula (1) - X can be any suitable counterion and is not particularly limited, but may be selected from the group consisting of hydroxide ions, halide ions (e.g., fluoride ions, chloride ions, bromide ions, iodide ions), nitrate ions, bisulfate ions, sulfamate ions, cyanide ions, and thiocyanate ions. Preferably, X -This is selected from the group consisting of hydroxide ions, halide ions, particularly chloride ions, and bromide ions.

[0034] More specific examples of the above-mentioned quaternary polyammonium salts include, but are not limited to, quaternary diammonium salts in which A in the above-mentioned general formula (1) is a substituted or unsubstituted linear or branched alkylene group having 1 to 30 carbon atoms, preferably 1 to 15 carbon atoms, and n is 1, i.e., quaternary diammonium salts having the following general formula (1a). 1 , R 2 , R 3 , R 4 , R 5 , R 6 and X - This is as explained above in relation to general formula (1). [ka] The specific examples of the cation moiety constituting the quaternary diammonium salt are not particularly limited, but include, for example, methylenebis(trimethylammonium) ion, methylenebis(ethyldimethylammonium) ion, methylenebis(dimethylpropylammonium) ion, methylenebis(triethylammonium) ion, ethylenebis(trimethylammonium) ion, ethylenebis(ethyldimethylammonium) ion, ethylenebis(dimethylpropylammonium) ion, ethylenebis(triethylammonium) ion, trimethylenebis(trimethylammonium) ion, trimethylenebis(ethyldimethylammonium) ion, trimethylenebis(dimethylpropylammonium) ion, trimethylenebis(triethylammonium) ion, tetramethylenebis(trimethylammonium) ion, tetramethylenebis(ethyldimethylammonium) ion, tetramethylenebis(dimethylpropylammonium) ion, tetramethylenebis(triethylammonium) ion, pentamethylenebis(trimethylammonium) ion, pentamethylenebis(ethyldimethylammonium) (Dimethylammonium) ion, pentamethylenebis(dimethylpropylammonium) ion, pentamethylenebis(triethylammonium) ion, hexamethylenebis(trimethylammonium) ion, hexamethylenebis(ethyldimethylammonium) ion, hexamethylenebis(dimethylpropylammonium) ion, hexamethylenebis(triethylammonium) ion, heptamethylenebis(trimethylammonium) ion, heptamethylenebis(ethyldimethylammonium) ion, heptamethylenebis(dimethylpropylammonium) Monium) ion, heptamethylenebis(triethylammonium) ion, octamethylenebis(trimethylammonium) ion, octamethylenebis(ethyldimethylammonium) ion, octamethylenebis(dimethylpropylammonium) ion, octamethylenebis(triethylammonium) ion, nonamethylenebis(trimethylammonium) ion, nonamethylenebis(ethyldimethylammonium) ion, nonamethylenebis(dimethylpropylammonium) ion, nonamethylenebis(triethylammonium) ion,Decamethylenebis(trimethylammonium) ion, decamethylenebis(ethyldimethylammonium) ion, decamethylenebis(dimethylpropylammonium) ion, decamethylenebis(triethylammonium) ion, undecamethylenebis(trimethylammonium) ion, undecamethylenebis(ethyldimethylammonium) ion, undecamethylenebis(dimethylpropylammonium) ion, undecamethylenebis(triethylammonium) ion, dodecamethylenebis(trimethylammonium) ion, dodecamethylenebis(ethyldimethylammonium) ion, dodecamethylenebis(dimethylpropylammonium) ion, dodecamethylenebis(triethylammonium) ion, tridecamethylenebis( It contains methylammonium ions, tridecamethylenebis(ethyldimethylammonium) ions, tridecamethylenebis(dimethylpropylammonium) ions, tridecamethylenebis(triethylammonium) ions, tetradecamethylenebis(trimethylammonium) ions, tetradecamethylenebis(ethyldimethylammonium) ions, tetradecamethylenebis(dimethylpropylammonium) ions, tetradecamethylenebis(triethylammonium) ions, pentadecamethylenebis(trimethylammonium) ions, pentadecamethylenebis(ethyldimethylammonium) ions, pentadecamethylenebis(dimethylpropylammonium) ions, and pentadecamethylenebis(triethylammonium) ions.

[0035] In certain embodiments of the present invention, the quaternary diammonium salt is a halide containing the above-mentioned hexamethylenebis(trimethylammonium) ion and decamethylenebis(trimethylammonium) ion, more specifically hexamethylenebis(trimethylammonium chloride) and decamethylenebis(trimethylammonium bromide).

[0036] Furthermore, the alkyl group in the cationic moiety exemplified above may or may not be substituted with halogen atoms (e.g., fluorine, chlorine, bromine, iodine), hydroxyl groups, amino groups, alkylamino groups (e.g., methylamino group, ethylamino group), dialkylamino groups (e.g., dimethylamino group, diethylamino group), etc. For example, the quaternary diammonium salt containing the hexamethylenebis(dimethylpropylammonium) ion exemplified above is given by the following formula (1b): [ka] As shown, the propyl group bonded to the nitrogen atom may be replaced with a chlorine atom or a hydroxyl group in the form of a halogen.

[0037] Other, more specific examples of quaternary polyammonium salts include, but are not limited to, the following general formula (1c): [ka] Represented by (wherein n' is an integer from 2 to 11), it includes quaternary polyammonium salts having a dimethylamino group at the end. This quaternary polyammonium salt is represented by R in general formula (1). 1 However, it is an n-propyl group substituted with a chlorine atom and a hydroxyl group, R 2 , R 3 , R 4 and R 5 is a methyl group, R 6 A is an n-propyl group substituted with a hydroxyl group, and the terminal portion is further substituted with a dimethylamino group, and A is an n-propylene group substituted with a hydroxyl group, and X - Cl - This corresponds to the compound. The compounds represented by the above general formulas (1) and (1a) to (1c), and the compounds specifically exemplified in relation to these general formulas, may be synthesized by any method known to those skilled in the art, or they may be commercially available.

[0038] [Quaternary ammonium salts with 6 or more carbon atoms] The quaternary ammonium salts having 6 or more carbon atoms are not particularly limited. For example, the following general formula (2): [Chemical formula] may be included. In the formula, R 7 , R 8 and R 9 are independently a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms or a benzyl group. Preferably, R 7 , R 8 and R 9 are methyl groups, or R 7 and R 8 are methyl groups and R 9 is a benzyl group. R 10 is a substituted or unsubstituted linear or branched alkyl group having 2 to 30 carbon atoms. Preferably, it is an unsubstituted linear or branched alkyl group having 2 to 30 carbon atoms. Y - is a counter ion, preferably a halide ion.

[0039] R 7 , R 8 and R 9 in the general formula (2) may independently be a substituted or unsubstituted 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, or benzyl group. R 7 , R 8 and R 9 may be substituted, for example, with a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl group, amino group, alkylamino group (e.g., methylamino group, ethylamino group), dialkylamino group (e.g., dimethylamino group, diethylamino group), etc., or may not be substituted. In a specific embodiment of the present invention, R 7 , R 8 and R 9These are methyl, ethyl, n-propyl, n-butyl, or benzyl groups, and these groups may be substituted with halogen atoms, hydroxyl groups, etc.

[0040] R in general formula (2) 10 This may be any linear or branched alkyl group having 2 to 30 carbon atoms, and this alkyl group may or may not be substituted with, for example, halogen atoms (e.g., fluorine, chlorine, bromine, iodine), hydroxyl groups, amino groups, alkylamino groups (e.g., methylamino group, ethylamino group), dialkylamino groups (e.g., dimethylamino group, diethylamino group), etc. 10More specific examples include, for example, substituted or unsubstituted ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, sec-butyl groups, tert-butyl groups, n-pentyl groups, isopentyl groups, sec-pentyl groups, tert-pentyl groups, neopentyl groups, n-hexyl groups, isohexyl groups, sec-hexyl groups, tert-hexyl groups, n-heptyl groups, isoheptyl groups, sec-heptyl groups, tert-heptyl groups, n-octyl groups, isooctyl groups, sec- Octyl group, tert-octyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, n-undecyl group, isoundecyl group, sec-undecyl group, tert-undecyl group, neoundecyl group, n-dodecyl group, isododecyl group, sec-dodecyl group, tert-dodecyl group, neododecyl group, n-tridecyl group, isotridecyl group, sec-tridecyl group, tert-tridecyl Isotetradecyl group, neotridecyl group, n-tetradecyl group, isotetradecyl group, sec-tetradecyl group, tert-tetradecyl group, neotetradecyl group, 1-isobutyl-4-ethyloctyl group, n-pentadecyl group, isopentadecyl group, sec-pentadecyl group, tert-pentadecyl group, neopentadecyl group, n-hexadecyl group, isohexadecyl group, sec-hexadecyl group, tert-hexadecyl group, neohexadecyl group, 1-methylpentadecyl group, n-heptadecyl This includes syl groups, isoheptadecyl groups, sec-heptadecyl groups, tert-heptadecyl groups, neoheptadecyl groups, n-octadecyl groups, isooctadyl groups, sec-octadecyl groups, tert-octadecyl groups, neoooctadyl groups, n-nonadecyl groups, isononadecyl groups, sec-nonadecyl groups, tert-nonadecyl groups, neonononadecyl groups, 1-methyloctyl groups, n-icosyl groups, isoicosyl groups, sec-icosyl groups, tert-icosyl groups, and neoicosyl groups. In a particular embodiment of the present invention, R 10 This group is an ethyl group, an n-propyl group, an n-butyl group, or a linear alkyl group having 8 to 18 carbon atoms, and these groups may be substituted with halogen atoms, hydroxyl groups, etc.

[0041] Quaternary ammonium salts with larger cationic moieties are considered effective in reducing the raised portion at the HLM periphery. Therefore, from the viewpoint of reducing the raised portion at the HLM periphery, R 7 ~R 9 Each of these is preferably a relatively long or bulky alkyl group, for example, a linear or branched alkyl group having 3 or more carbon atoms, particularly 4 or more carbon atoms. Alternatively or in addition thereto, for similar reasons, R 10 It is preferable that the alkyl group is a long-chain or bulky alkyl group, for example, a linear or branched alkyl group having 7 or more carbon atoms, particularly 8 or more carbon atoms. Also, from the viewpoint of reducing the raised portion around the HLM, 7 ~R 10 The total number of carbon atoms is preferably 10 or more, and more preferably 15 or more. On the other hand, the upper limit of the number of carbon atoms is not particularly limited, but is generally 50 or less, for example, 45 or less or 40 or less.

[0042] Y in general formula (2) - X can be any suitable counterion and is not particularly limited, but may be selected from the group consisting of hydroxide ions, halide ions (e.g., fluoride ions, chloride ions, bromide ions, iodide ions), nitrate ions, bisulfate ions, sulfamate ions, cyanide ions, and thiocyanate ions. Preferably, X - This is selected from the group consisting of hydroxide ions, halide ions, particularly chloride ions, and bromide ions.

[0043] The specific examples of the cation moieties constituting the above-mentioned quaternary ammonium salts having 6 or more carbon atoms are not particularly limited, but include, for example, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, methyltriethylammonium ion, methyltripropylammonium ion, methyltributylammonium ion, methyltripentylammonium ion, methyltrihexylammonium ion, ethyltripropylammonium ion, ethyltributylammonium ion, ethyltripentylammonium ion, ethyltrihexylammonium ion, diethyldimethylammonium ion, propyltrimethylammonium ion, propyltriethylammonium ion, propyltributylammonium ion, propyltripentylammonium ion, propyltrihexylammonium ion, dipropyldimethylammonium ion, dipropyldiethylammonium ion, butyltrimethylammonium ion, butyltri Lipropylammonium ion, butyltripentylammonium ion, butyltrihexylammonium ion, dibutyldimethylammonium ion, dibutyldiethylammonium ion, dibutyldipropylammonium ion, pentyltrimethylammonium ion, pentyltriethylammonium ion, pentyltripropylammonium ion, pentyltributylammonium ion, pentyltrihexylammonium ion, dipentyldimethylammonium ion, dipentyldiethylammonium ion, dipentyldipropylammonium ion, dipentyldibutylammonium ion, dipentyldibutylammonium ion, hexyltrimethylammonium ion, hexyltriethylammonium ion, hexyltripropylammonium ion, hexyltributylammonium ion, hexyltripentylammonium ion, dihexyldimethylammonium ion, dihexyldiethylammonium ion, dihexyldipropylammonium ion, dihexyldibutylammonium ion, dihexyldipentylammonium ion, heptyltrimethylammonium ion,This product contains heptyltriethylammonium ion, heptyltripropylammonium ion, heptyltributylammonium ion, octyltrimethylammonium ion, octyltriethylammonium ion, octyltripropylammonium ion, octyltributylammonium ion, nonyltrimethylammonium ion, nonyltriethylammonium ion, nonyltripropylammonium ion, nonyltributylammonium ion, decyltrimethylammonium ion, undecyltrimethylammonium ion, dodecyltrimethylammonium ion, tridecyltrimethylammonium ion, tetradecyltrimethylammonium ion, pentadecyltrimethylammonium ion, hexadecyltrimethylammonium ion, heptadecyltrimethylammonium ion, octadecyltrimethylammonium ion, nonadecyltrimethylammonium ion, eicosyltrimethylammonium ion, benzylethyldimethylammonium ion, benzyltriethylammonium ion, benzyltripropylammonium ion, benzyltributylammonium ion, benzyltripentylammonium ion, benzyltrihexylammonium ion, and benzalkonium ion.

[0044] In certain embodiments of the present invention, the quaternary ammonium salt having 6 or more carbon atoms is a hydroxide or halide containing tetraethylammonium ions, tetrabutylammonium ions, octyltrimethylammonium ions, hexadecyltrimethylammonium ions, and benzalkonium ions, and more specifically, tetraethylammonium hydroxide, tetraethylammonium chloride, tetrabutylammonium hydroxide, octyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, and benzalkonium chloride. The compounds represented by the above general formula (2) and the compounds specifically exemplified in relation to said general formula may be synthesized by any method known to those skilled in the art or may be commercially available.

[0045] [Alkylated polymer having an amide structure] Alkylated polymers having an amide structure include, for example, any copolymer of a compound having an amide structure and an unsaturated hydrocarbon having at least one double bond. The molar ratio of the compound having an amide structure to the unsaturated hydrocarbon having at least one double bond is not particularly limited and can be selected within any suitable range, but is generally 99:1 to 50:50, and may be, for example, 95:5 to 70:30, or 95:5 to 80:20. Specific examples of compounds having an amide structure are not particularly limited, but include, for example, N-vinylpyrrolidone, acryloylmorpholine, dimethylacrylamide, N-vinylacetamide, and their derivatives. Preferably, the compound having an amide structure is a compound having a cyclic amide structure, specifically including N-vinylpyrrolidone and its derivatives, such as N-vinyl-3-methylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinyl-3,3,5-trimethylpyrrolidone, and N-vinyl-3-benzylpyrrolidone. Specific examples of unsaturated hydrocarbons having at least one double bond are not particularly limited, but include, for example, unsaturated hydrocarbons having 2 or more carbon atoms, generally 2 to 10 carbon atoms, such as ethylene, propylene, butene (1-butene, cis-2-butene, trans-2-butene, isobutene), pentene (1-pentene, cis-2-pentene, trans-2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene), etc.

[0046] In the present invention, the alkylated polymer having an amide structure can have any suitable molecular weight. While not particularly limited, the alkylated polymer having an amide structure can, for example, have an average molecular weight of about 500 to about 1,000,000.

[0047] In certain embodiments of the present invention, the alkylated polymer having an amide structure is alkylated polyvinylpyrrolidone, and more specifically, butylated polyvinylpyrrolidone (butylated PVP), which is a copolymer of N-vinylpyrrolidone and butene, particularly 1-butene. The alkylated polymer having an amide structure described above and the compounds specifically illustrated in connection therewith may be synthesized by any method known to those skilled in the art or may be commercially available.

[0048] [Water-based carrier] The aqueous carrier is used to facilitate the application of all components dissolved or suspended in the aqueous carrier to a suitable substrate surface to be polished. The aqueous carrier may typically consist of water alone, water and a water-soluble solvent, or an emulsion. Preferred water-soluble solvents include alcohols, such as methanol and ethanol. The aqueous carrier is preferably water, more preferably deionized water.

[0049] The chemical mechanical polishing composition of the present invention can have any suitable pH, and the specific pH value can be appropriately determined considering the polishing speed, etc. For example, the chemical mechanical polishing composition can have a pH of 7 to 12, preferably 8 to 12, and more preferably 8.5 to 12. The pH value can be adjusted by adding a pH adjusting agent as needed. The pH adjusting agent may be any alkaline substance, and may be the same as or different from the basic component described above. Preferably, the pH adjusting agent is selected from the group consisting of ammonia, potassium hydroxide, sodium hydroxide, ammonium carbonate, potassium carbonate, and sodium carbonate. More preferably, the pH adjusting agent is ammonia, potassium hydroxide, or sodium hydroxide, and most preferably ammonia.

[0050] The chemical mechanical polishing composition of the present invention may optionally contain a pH buffer. Preferably, the pH buffer is selected from the group consisting of ammonium bicarbonate, potassium bicarbonate, and sodium bicarbonate. More preferably, the pH adjuster is potassium bicarbonate or sodium bicarbonate.

[0051] [Additional ingredients] The chemical mechanical polishing composition of the present invention may optionally further contain tetramethylammonium hydroxide. Further addition of tetramethylammonium hydroxide can improve the polishing speed of the substrate.

[0052] Tetramethylammonium hydroxide may be present in the chemical mechanical polishing composition in an amount of, for example, 0.001% by mass or more, 0.002% by mass or more, 0.005% by mass or more, 0.01% by mass or more, or 0.1% by mass or more, based on the mass of the aqueous carrier and the total components dissolved or suspended therein, and in an amount of 10.0% by mass or less, 5.0% by mass or less, 3.0% by mass or less, 1.0% by mass or less, or 0.5% by mass or less. Tetramethylammonium hydroxide may be present in the chemical mechanical polishing composition in an amount of preferably 0.001 to 10.0% by mass, more preferably 0.005 to 5.0% by mass, and most preferably 0.01 to 3.0% by mass.

[0053] [Water-soluble polymer] The chemical mechanical polishing composition of the present invention may optionally further contain a water-soluble polymer different from the alkylated polymer having the amide structure described above. Such a water-soluble polymer is not particularly limited, but examples include at least one selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinylacetamide, cellulose derivatives, and polymers containing polyvinyl alcohol structural units. In particular, further addition of polyvinylpyrrolidone and / or polyvinylacetamide to the chemical mechanical polishing composition of the present invention makes it possible to achieve a higher haze reduction effect compared to the case without their addition. Furthermore, the addition of polyvinylpyrrolidone and / or polyvinylacetamide can also reduce the formation of defects on the substrate surface. Therefore, compositions containing these water-soluble polymers can be effectively used not only in the pre-polishing step but also in the rinsing and finish polishing steps after the pre-polishing step. Polyvinylpyrrolidone and polyvinylacetamide can have any suitable molecular weight. While not particularly limited, polyvinylpyrrolidone and polyvinylacetamide can have an average molecular weight of, for example, about 500 to about 1,000,000.

[0054] In certain preferred embodiments of the present invention, the water-soluble polymers described above include polymers that further contain cellulose derivatives and / or polyvinyl alcohol structural units, in addition to polyvinylpyrrolidone and / or polyvinylacetamide. Each of the polymers containing cellulose derivatives and polyvinyl alcohol structural units will be described in detail below.

[0055] [Cellulose derivatives] An optional cellulose derivative acts primarily as a wetting agent in the chemical mechanical polishing composition of the present invention. Such a wetting agent is effective in maintaining the hydrophilicity of the surface of a substrate such as a silicon wafer. In the present invention, the cellulose derivative can be selected from, for example, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and any combination thereof, and hydroxyethylcellulose is preferred. The cellulose derivative can have an average molecular weight of 50,000 to 2,000,000.

[0056] The cellulose derivative may be present in the chemical mechanical polishing composition in an amount of, for example, 0.001% by mass or more, 0.002% by mass or more, 0.005% by mass or more, or 0.01% by mass or more, and 2.0% by mass or less, 1.5% by mass or less, 1.2% by mass or less, or 1.0% by mass or less, based on the mass of the aqueous carrier and the total components dissolved or suspended therein. The cellulose derivative may be present in the chemical mechanical polishing composition in an amount of preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.5% by mass, and most preferably 0.01 to 1.0% by mass.

[0057] [Polyvinyl alcohol structural units containing polymers] In chemical mechanical polishing, mechanical interaction is utilized between the substrate and the polishing composition (slurry). Therefore, continuous surface defects such as nanoscratch and PID may occur on the substrate during polishing due to abrasives contained in the slurry and / or other particles aggregated in the slurry. In the present invention, in order to reduce continuous surface defects such as nanoscratch and PID on the substrate, the chemical mechanical polishing composition may contain a polymer containing polyvinyl alcohol structural units.

[0058] Polymers containing polyvinyl alcohol structural units can also function as wetting agents. Therefore, in the chemical mechanical polishing composition of the present invention, polymers containing polyvinyl alcohol structural units may be used in place of or in addition to cellulose derivatives to maintain the hydrophilicity of the substrate surface. Cellulose derivatives have the problem of being very difficult to maintain quality stability because they are derived from natural cellulose.

[0059] The polymer containing polyvinyl alcohol structural units may be any polymer containing polyvinyl alcohol structural units. For example, the polymer containing polyvinyl alcohol structural units may simply be polyvinyl alcohol, or it may contain polyalkylene oxides such as polyethylene glycol in addition to polyvinyl alcohol. Furthermore, the polymer containing polyvinyl alcohol structural units may, for example, have polyvinyl alcohol structural units in the main chain or side chains of the polymer, and furthermore, a portion of the polyvinyl alcohol structural units may be substituted with acyloxy groups. An example of a polymer having polyvinyl alcohol structural units in the main chain is a polyvinyl alcohol-polyalkylene oxide graft copolymer having polyvinyl alcohol structural units in the main chain and polyalkylene oxide structural units in the side chains, wherein the polyalkylene oxide structural units may contain at least one selected from the group consisting of ethylene oxide, propylene oxide, and combinations thereof. In such copolymers, polyvinyl alcohol structural units and polyalkylene oxide structural units may be present in a molar ratio, for example, in the range of 95:5 to 60:40 or 90:10 to 70:30.

[0060] A preferred example of such a copolymer is, for example, the following general formula (3): [ka] It is expressed as, in the formula, R 11R is a hydroxyl group, or an acyloxy group represented as R'COO- (wherein R' is a C1-C8 alkyl group) (for example, a CH3COO- group), 12 A polyvinyl alcohol-polyethylene oxide graft copolymer is characterized by a hydrogen atom or an acyl group represented by R''CO- (wherein R'' is a C1-C8 alkyl group) (e.g., a CH3CO- group), a is an integer from 1 to 10,000, M1 and M2 are real numbers greater than 0 mol% and less than 100 mol%, and M1 + M2 = 100 mol%. The copolymer of general formula (3) is R 11 The structure may consist of a mixture of hydroxyl and acyloxy groups, and more specifically, a structure in which some of the acyloxy groups are saponified into hydroxyl groups. The degree of saponification in this case is not particularly limited, but may be 70-100%, 80-100%, 90-100%, or 95-100%. The values ​​of M1 and M2 can be appropriately determined according to the ratio of polyvinyl alcohol structural units constituting the main chain and polyethylene oxide structural units constituting the side chains.

[0061] A more specific example of the polyvinyl alcohol-polyethylene oxide graft copolymer of general formula (3) is the following general formula (3a): [ka] A polyvinyl alcohol-polyethylene oxide graft copolymer is given by the formula, where a is an integer between 1 and 10,000, M1 and M2 are real numbers greater than 0 mol% and less than 100 mol%, and M1 + M2 = 100 mol%. In general formula (3a), the hydroxyl groups of the polyvinyl alcohol structural units constituting the main chain may be partially substituted with acyloxy groups represented by R'COO- (wherein R' is a C1-C8 alkyl group), and similarly, the terminal hydroxyl groups of the polyethylene oxide structural units constituting the side chain in general formula (3a) may be partially substituted with acyl groups represented by R''CO- (wherein R'' is a C1-C8 alkyl group).

[0062] On the other hand, an example of a polymer containing polyvinyl alcohol structural units in its side chains is a polyvinyl alcohol-polyalkylene oxide graft copolymer containing polyalkylene oxide structural units in its main chain and polyvinyl alcohol structural units in its side chains. The polyalkylene oxide structural units may contain at least one selected from the group consisting of ethylene oxide, propylene oxide, and combinations thereof. In such a copolymer, the polyvinyl alcohol structural units and polyalkylene oxide structural units may be present in a molar ratio, for example, in the range of 95:5 to 60:40 or 90:10 to 70:30.

[0063] A preferred example of such a copolymer is, for example, the following general formula (4): [ka] It is expressed as, in the formula, R 13 R is a hydroxyl group, or an acyloxy group represented as R'COO- (wherein R' is a C1-C8 alkyl group) (for example, a CH3COO- group), 14 and R 15 A polyvinyl alcohol-polyethylene oxide graft copolymer is described, in which each is independently a linear or branched C2-C3 alkylene group, b is an integer between 2 and 10,000, N1 and N2 are real numbers greater than 0 mol% and less than 100 mol%, and N1 + N2 = 100 mol%. The copolymer of general formula (4) may have a structure in which hydroxyl groups and acyloxy groups are mixed with R, and more specifically, a structure in which some of the acyloxy groups are saponified to hydroxyl groups. In this case, the degree of saponification is not particularly limited, but may be 70-100%, 80-100%, 90-100%, or 95-100%. The values ​​of N1 and N2 can be appropriately determined according to the ratio of polyethylene oxide structural units constituting the main chain and polyvinyl alcohol structural units constituting the side chains.

[0064] A more specific example of the polyvinyl alcohol-polyethylene oxide graft copolymer of general formula (4) is the following general formula (4a): [ka] Examples of polyvinyl alcohol-polyethylene oxide graft copolymers are those represented by the formula, where b is an integer between 2 and 10,000, N1 and N2 are real numbers greater than 0 mol% and less than 100 mol%, and N1 + N2 = 100 mol%. In general formula (4a), the hydroxyl groups of the polyvinyl alcohol structural units constituting the side chains may be partially substituted with acyloxy groups represented by R'COO- (wherein R' is a C1-C8 alkyl group).

[0065] When the polymer containing polyvinyl alcohol structural units is polyvinyl alcohol or a mixture of polyvinyl alcohol and polyalkylene oxide, the polyvinyl alcohol and polyalkylene oxide can have an average molecular weight of, for example, 1,000 to 10,000,000. On the other hand, when the polymer containing polyvinyl alcohol structural units is the above-mentioned polyvinyl alcohol-polyethylene oxide graft copolymer, the polyvinyl alcohol-polyethylene oxide graft copolymer can have an average molecular weight of, for example, 5,000 to 500,000, 10,000 to 300,000, or 10,000 to 200,000.

[0066] Polymers containing polyvinyl alcohol structural units may be present in the chemical mechanical polishing composition in amounts of, for example, 0.1 ppm or more, 1 ppm or more, 2 ppm or more, or 5 ppm or more, and 5000 ppm or less, 3000 ppm or less, 1000 ppm or less, or 500 ppm or less, based on the mass of the aqueous carrier and the total components dissolved or suspended therein. Polymers containing polyvinyl alcohol structural units may be present in the chemical mechanical polishing composition in amounts of preferably 0.1 to 5000 ppm (0.00001 to 0.5 mass%), more preferably 1 to 3000 ppm (0.0001 to 0.3 mass%), and most preferably 2 to 1000 ppm (0.0002 to 0.1 mass%).

[0067] [Other additives] The chemical mechanical polishing composition of the present invention may optionally further contain other additives, such as polishing speed accelerators and chelating agents. Examples of polishing speed accelerators include hydroxamic acid (e.g., acetohydroxamic acid), nitrogen-containing heterocyclic compounds (e.g., triazoles such as 1,2,4-triazole), or combinations thereof. Examples of chelating agents include organic acids such as oxalic acid, citric acid, malonic acid, succinic acid, glutaric acid, adipic acid, tartaric acid, and phthalic acid; amino acids such as glycine, serine, proline, leucine, alanine, asparagine, glutamine, valine, and lysine; and polyamine complexes such as ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid, iminodiacetic acid, and diethylenetriaminepentaacetic acid (DTPA).

[0068] [Rinse composition] The rinse composition of the present invention is At least one compound selected from the group consisting of quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure, and Water-based carrier It is characterized by containing [something].

[0069] By washing the substrate after chemical mechanical polishing with the rinse composition of the present invention, abrasives and the like remaining on the polishing pad can be removed, and the same effects as those of the chemical mechanical polishing composition of the present invention can be achieved. More specifically, the raised portion around the hard laser marks can be reduced, particularly in pre-polishing, and / or the haze on the substrate surface can be reduced in both pre-polishing and finish polishing. The at least one compound may include two or more of the following: quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, and alkylated polymers having an amide structure. Details of the quaternary polyammonium salts, quaternary ammonium salts having 6 or more carbon atoms, alkylated polymers having an amide structure, and aqueous carriers are as previously described for the chemical mechanical polishing composition of the present invention.

[0070] Furthermore, the rinse composition of the present invention may optionally further contain tetramethylammonium hydroxide. Tetramethylammonium hydroxide may be present in the rinse composition in an amount of, for example, 0.001% by mass or more, 0.002% by mass or more, 0.005% by mass or more, 0.01% by mass or more, or 0.1% by mass or more, based on the mass of the aqueous carrier and the total components dissolved or suspended therein, and in an amount of 10.0% by mass or less, 5.0% by mass or less, 3.0% by mass or less, 1.0% by mass or less, or 0.5% by mass or less. Tetramethylammonium hydroxide may be present in the rinse composition in an amount of preferably 0.001 to 10.0% by mass, more preferably 0.005 to 5.0% by mass, and most preferably 0.01 to 3.0% by mass.

[0071] Furthermore, the rinse composition of the present invention may optionally further contain a water-soluble polymer different from the alkylated polymer having the amide structure described above. Such a water-soluble polymer is not particularly limited, but examples include at least one selected from the group consisting of polyvinylpyrrolidone, polyvinylacetamide, cellulose derivatives, and polymers containing polyvinyl alcohol structural units. In particular, further addition of polyvinylpyrrolidone and / or polyvinylacetamide to the rinse composition of the present invention makes it possible to achieve a higher haze reduction effect compared to the absence of these additions. Polyvinylpyrrolidone and polyvinylacetamide can have any suitable molecular weight. While not particularly limited, polyvinylpyrrolidone and polyvinylacetamide can, for example, have an average molecular weight of about 500 to about 1,000,000.

[0072] In certain preferred embodiments of the present invention, the water-soluble polymer further comprises a polymer containing a cellulose derivative and / or polyvinyl alcohol structural unit, in addition to polyvinylpyrrolidone and / or polyvinylacetamide. Details of the polymer containing the cellulose derivative and polyvinyl alcohol structural unit used in the rinse composition of the present invention are as previously described for the chemical mechanical polishing composition of the present invention. The rinse composition of the present invention may also optionally further contain other additives. Details of such other additives are also as previously described for the chemical mechanical polishing composition of the present invention.

[0073] [Methods for chemical and mechanical polishing and rinsing of substrates] The chemical mechanical polishing composition and rinse composition of the present invention can be used not only in single-sided polishing, which polishes only one side of the substrate, but also in double-sided polishing, which polishes both sides of the substrate. Although not particularly limited, for example, when removing raised portions around hard laser marks, it is preferable to use the chemical mechanical polishing composition and rinse composition of the present invention in the preliminary polishing step in double-sided polishing. On the other hand, when the main objective is to reduce haze, it is preferable to use it in the finish polishing step in single-sided polishing. The following describes in detail the methods for using the chemical mechanical polishing composition and rinse composition of the present invention in single-sided polishing and double-sided polishing, respectively.

[0074] [Chemical mechanical polishing method for substrates in single-sided polishing] The chemical mechanical polishing method for the substrate of the present invention is A step of bringing the substrate into contact with the polishing pad and the chemical mechanical polishing composition described above, The process of moving the polishing pad with respect to the substrate and the chemical mechanical polishing composition between them, and A step of polishing the substrate by abrading at least a portion of it. It is characterized by containing [something].

[0075] The present invention's method for chemically mechanically polishing one side of a substrate is applied in a chemical mechanical polishing (CMP) apparatus suitable for polishing one side of a substrate. Typically, this apparatus includes a platen having a velocity resulting from movement, orbital motion, linear motion or circular motion during use; a polishing pad in contact with the platen and moving with the platen as the platen moves; and a carrier that holds the substrate to be polished by contacting and moving against the surface of the polishing pad. Polishing of the substrate is performed by bringing the substrate into contact with the polishing pad and the chemical mechanical polishing composition of the present invention, and then moving the polishing pad against the substrate to polish the substrate by abrading at least a portion of it.

[0076] The substrate can be planarized or polished with a chemical mechanical polishing composition along with any suitable polishing pad. The substrate may be not only a silicon substrate, but also a silicon substrate on which a polysilicon film, SiO2 film, or metal wiring film is formed, a sapphire substrate, a SiC substrate, a GaAs substrate, a GaN substrate, a substrate for TSV formation, and a low-resistivity substrate with a resistivity of less than 1 Ω·cm, particularly less than 0.010 Ω·cm or less than 0.002 Ω·cm, particularly a low-resistivity silicon substrate. Suitable polishing pads include, for example, woven and non-woven polishing pads. Furthermore, suitable polishing pads may contain any suitable polymer with various densities, hardness, thickness, compressibility, resilience to compression, and compressive modulus. Suitable polymers include, for example, polyvinyl chloride, polyvinyl fluoride, nylon, carbon fluoride, polycarbonate, polyester, polyacrylate, polyether, polyethylene, polyamide, polyurethane, polystyrene, polypropylene, their co-formed products, and mixtures thereof. The polishing pad should be appropriately selected according to the type of substrate and the application, such as pre-polishing or finish polishing.

[0077] The method of the present invention can be carried out in addition to a method in which a slurry of a chemical mechanical polishing composition is prepared in advance and the slurry is supplied to a substrate while polishing with a polishing pad, or in a method in which a diluent and a slurry concentrate are supplied onto a polishing pad and a polishing slurry is prepared near the polishing pad.

[0078] [Rinsing method for substrates in single-sided polishing] The present invention provides a method for rinsing a substrate, A step of bringing the substrate after chemical mechanical polishing into contact with a polishing pad and the rinse composition described above, and The process of moving the polishing pad with the rinse composition between the substrate and the substrate. It is characterized by containing [something].

[0079] By cleaning the substrate after chemical mechanical polishing using the rinse composition of the present invention and the method described above, it is possible to remove abrasives and the like remaining on the polishing pad and achieve the same effects as the chemical mechanical polishing composition of the present invention. More specifically, it is possible to reduce the raised portion around the hard laser marks, especially in pre-polishing, and / or reduce the haze on the substrate surface in both pre-polishing and finish polishing. Details of the CMP apparatus used in this method, as well as the substrate and polishing pad, etc., are as previously described in the chemical mechanical polishing method for the substrate.

[0080] [Chemical mechanical polishing method for substrates in double-sided polishing] The chemical mechanical polishing method for the substrate of the present invention is A method for chemical mechanical polishing of a substrate using a polishing apparatus comprising an upper platen and a lower platen, each to which a polishing pad is attached, and a carrier plate having at least one holding hole for holding the substrate, wherein The process involves holding the substrate in at least one holding hole of the carrier plate, and then sandwiching the carrier plate between the upper and lower plates to which polishing pads are attached, respectively, and A process in which the carrier plate is rotated and revolved while supplying the chemical mechanical polishing composition described above to the polishing surface of the substrate, thereby simultaneously polishing both sides of the substrate. It is characterized by containing [something].

[0081] The present invention's method for chemically mechanically polishing both sides of a substrate is applied in a chemical mechanical polishing (CMP) apparatus suitable for polishing both sides of a substrate. Typically, this apparatus comprises an upper platen and a lower platen, each to which a polishing pad is attached, and a carrier plate having at least one holding hole for holding the substrate. Multiple teeth are provided on the outer circumference of the carrier plate that holds the substrate, and the carrier plate is sandwiched between the upper and lower plates to which the polishing pads are attached, and the teeth of the carrier plate mesh with the teeth of a sun gear located on the center side of the lower platen and the teeth of an internal gear located on the outer circumference of the lower platen. That is, the carrier plate, sun gear, and internal gear constitute a planetary gear mechanism, and using this mechanism, the carrier plate can rotate in a manner corresponding to its rotation and revolution around the central axis of the platen, driven by the sun gear and internal gear.

[0082] Using such a CMP apparatus, for example, the chemical mechanical polishing composition of the present invention is supplied to the polishing surface of the substrate that is in contact with the lower surface of the upper platen and the upper surface of the lower platen, starting from the vicinity of the lower surface of the upper platen, while the carrier plate is rotated and revolved by the planetary gear mechanism described above, so that both sides of the substrate held by the carrier plate are polished simultaneously by polishing pads attached to the lower surface of the upper platen and the upper surface of the lower platen. Details of the substrate and polishing pads are as previously described in relation to single-sided polishing.

[0083] Furthermore, the method of the present invention can be carried out not only by preparing a slurry of a chemical mechanical polishing composition in advance and polishing with a polishing pad while supplying the slurry to a substrate, but also by supplying a diluent and a slurry concentrate onto a polishing pad and preparing a polishing slurry near the polishing pad.

[0084] [Rinsing method for substrates in double-sided polishing] The present invention provides a method for rinsing a substrate, A method for rinsing a substrate using a polishing apparatus comprising an upper platen and a lower platen, each having polishing pads attached to them, and a carrier plate having at least one holding hole for holding the substrate, A process of rotating and revolving the carrier plate while supplying the rinse composition described above to the polished surface of the substrate after chemical mechanical polishing. It is characterized by containing [something].

[0085] By cleaning the substrate after chemical mechanical polishing using the rinse composition of the present invention and the method described above, it is possible to remove abrasives and the like remaining on the polishing pad and achieve the same effects as the chemical mechanical polishing composition of the present invention. More specifically, it is possible to reduce the raised portion around the hard laser marks, especially in pre-polishing, and / or reduce the haze on the substrate surface in both pre-polishing and finish polishing. Details of the CMP apparatus used in this method, as well as the substrate and polishing pad, etc., have been previously described in relation to single-sided polishing.

[0086] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to these examples. [Examples]

[0087] In the following examples, various chemical mechanical polishing compositions according to the present invention were prepared, and their effects on reducing the raised portion of the HLM periphery and reducing haze on the surface of a silicon substrate when polished with them were investigated.

[0088] [Example A: Evaluation of HLM and haze characteristics, etc.] [Preparation of the polishing composition of Comparative Example 1] Comparative Example 1's polishing composition was prepared by adding 21% by mass of colloidal silica (average secondary particle size 50-60 nm), 0.79% by mass of potassium hydroxide (basic component), 2.3% by mass of tetramethylammonium hydroxide (TMAH), 1.31% by mass of potassium bicarbonate (pH buffer), 0.033% by mass of 1,2,4-triazole (corrosion inhibitor), and 0.39% by mass of diethylenetriaminepentaacetic acid (chelating agent) to water.

[0089] [Preparation of the polishing composition of Comparative Example 2] The polishing composition for Comparative Example 2 was prepared in the same manner as in Comparative Example 1, except that five times the amount of colloidal silica was added.

[0090] [Preparation of other abrasive compositions] Other polishing compositions were prepared in the same manner as in Comparative Example 1, except that various additive components listed in Table 1 below were added, TMAH was omitted or its content was changed as needed, and other water-soluble polymers (polyvinylpyrrolidone: molecular weight 40,000 or polyvinylacetamide: molecular weight 50,000) were added.

[0091] [Polishing operation] First, the HLM barcoded back side of a commercially available ground silicon wafer (resistivity 1 Ω·cm to less than 100 Ω·cm) was chemically and mechanically polished under the following conditions using a slurry prepared by diluting the polishing composition prepared above 21 times (by mass) with pure water. The pH of the diluted slurry was approximately 9.5 to 11. (1) CMP equipment: 12-inch single-sided polishing machine, Okamoto Machine Works SPP800S (2) Wafer head: Template method (3) Polishing pad: Nitta Haas MH S-15A (4) Plate rotation speed: 32 rpm (5) Polishing head rotation speed: 31 rpm (6) Polishing pressure: 1.45 psi = 102 g / cm² 2 = 10kPa (7) Slurry supply rate: 300 mL / min (flow-through) (8) Polishing time: 20 minutes

[0092] After polishing, the silicon wafers were batch-washed at 23°C for 20 minutes using SC-1 (a solution of ammonia (29% by mass aqueous solution): hydrogen peroxide (31% by mass aqueous solution): pure water = 2:1:10 (volume ratio)). Next, the silicon wafers were scrubbed at 23°C using SC-200S manufactured by Shibaura Mechatronics with SC-1 (a solution of ammonia (29% by mass aqueous solution): hydrogen peroxide (31% by mass aqueous solution): pure water = 1:4:20 (volume ratio)) and a PVA brush, followed by rinsing with pure water. The characteristics of the silicon wafer surface after washing were measured and evaluated by the following methods. The results are shown in Table 1 below.

[0093] [HLM elevation height] The height of the raised portion at the edge of the HLM (HLM elevation height) was measured using a tactile profiler (KLA Tencor P16) by scanning the top of the dots in the innermost row of the T7 marks of the SEMI standard. More specifically, the maximum height from the baseline plane of the wafer surface was determined as the HLM elevation height (Å), and this HLM elevation height was evaluated according to the following criteria, with ◎ and ○ indicating a pass and △ and × indicating a fail. ◎: Less than 0 Å (the raised portion has been completely removed) ○: 0 Å or higher, containing five times the amount (5.0%) of colloidal silica as an abrasive, and not containing the additive components according to the present invention, the HLM elevation height is less than or equal to that of Comparative Example 2. △: Less than 120% of the HLM elevation height in Comparative Example 2 ×: More than 120% of the HLM elevation height in Comparative Example 2

[0094] [Hayes] Haze was evaluated using a KLA Tencor Surfscan SP2, measured in the dark-field wide oblique incidence channel (DWO). More specifically, the obtained haze values ​​(ppm) were evaluated according to the following criteria, with ◎ and ○ indicating a pass, and △ and × indicating a fail. ◎: Less than 10 ppm ○: 10 ppm or more and less than 90% of the haze value of Comparative Example 1 which does not contain the additive component according to the present invention. △: The haze value is 90% or more of that of Comparative Example 1, and 110% or less. ×: Over 110% of the haze value in Comparative Example 1

[0095] [Si polishing rate] The Si polishing rate was determined by dividing the mass difference before and after polishing by the polishing time, and the obtained Si polishing rate (Å / min) was evaluated according to the following criteria. ◎: More than 100% of the Si polishing speed of Comparative Example 1, which does not contain the additive components according to the present invention. ○: 90% or more and 100% or less of the Si polishing speed of Comparative Example 1. △: Less than 90% of the Si polishing speed in Comparative Example 1

[0096] [Table 1]

[0097] Referring to Table 1, it can be seen that in all the polishing compositions of the examples containing the additive component according to the present invention, HLM characteristics equal to or better than those of Comparative Example 2 (the polishing composition of Comparative Example 2 contains five times the amount of colloidal silica as an abrasive and does not contain the additive component according to the present invention) and / or better than those of Comparative Example 1 which does not contain the additive component according to the present invention. Furthermore, as is clear from the results in Table 1, when the content of the additive component is the same, it can be seen that by using an additive component consisting of a quaternary (poly)ammonium salt having a larger cationic moiety, higher HLM characteristics can be achieved and the raised portion can be completely removed. Among these, the polishing compositions of Examples 3 and 4, which contain hexamethylenebis(trimethylammonium chloride) as an additive component, are more preferable because the Si polishing speed is better than that of the composition without additive (Comparative Example 1), despite the relatively low content of the additive component. Furthermore, in the polishing compositions of Examples 19 and 21, in which the additive component according to the present invention was combined with polyvinylpyrrolidone (PVP) or polyvinylacetamide, not only were higher HLM properties obtained, but excellent haze properties were also achieved simultaneously. Although not shown in Table 1, in the polishing compositions of Examples 19 and 21 using PVP or polyvinylacetamide, and in Example 20 using butylated PVP, a tendency to reduce the formation of light point defects (LPDs) on the substrate surface was also observed. These compositions containing water-soluble polymers exhibit excellent haze and LPD properties and can therefore be effectively used not only in the pre-polishing process but also in the rinsing and finish polishing processes after the pre-polishing process.

[0098] In contrast, the polishing composition of Comparative Example 1, which did not contain the additive component according to the present invention, exhibited low HLM properties, and similarly, the polishing composition of Comparative Example 2, which also did not contain the additive component according to the present invention, failed to achieve sufficient haze properties. Furthermore, the polishing composition of Comparative Example 7, which used ethyltrimethylammonium hydroxide, equivalent to a quaternary ammonium salt with 5 carbon atoms, as an additive component, exhibited low HLM properties and failed to achieve sufficient haze properties.

[0099] [Example B: Polishing of low-resistivity silicon substrates] In this example, the polishing characteristics of the chemical mechanical polishing composition of the present invention were investigated when used to polish a low-resistivity silicon substrate (8-inch diameter size) with a resistivity of less than 0.01 Ω·cm.

[0100] [Preparation of the comparative abrasive composition] Comparative abrasive compositions were prepared by adding a predetermined amount of colloidal silica (average secondary particle size 50 nm or 70 nm), ammonia (basic component), and optionally tetramethylammonium hydroxide (TMAH), hydroxyethylcellulose, and / or polyvinyl alcohol-polyethylene oxide graft copolymer having general formula (3a) (polyvinyl alcohol:polyethylene oxide = 80:20 mol%, molecular weight: 93,600, degree of saponification: 98.5%) to water.

[0101] [Preparation of the polishing composition in the example] The polishing composition of the example was prepared in the same manner as in the comparative example, except that a predetermined amount of hexamethylenebis(trimethylammonium chloride) was added.

[0102] [Polishing operation] The low-resistivity silicon substrate described above was subjected to chemical mechanical polishing under the following conditions using a slurry prepared by diluting the polishing composition prepared above with pure water so that the content of each component was as shown in Table 2 below. The pH of the diluted slurry was approximately 9.5 to 11. (1) CMP equipment: 8-inch single-sided polishing machine, Okamoto Machine Works SPP800S (2) Wafer head: Template method (3) Polishing pad (pre-polishing): Nitta Haas SUBA840 Polishing pad (finishing): Nitta Haas SPM3100 (4) Plate rotation speed (pre-polishing): 49 rpm Plate rotation speed (finishing): 50 rpm (5) Polishing head rotation speed (pre-polishing): 47 rpm Polishing head rotation speed (finishing): 49 rpm (6) Polishing pressure: 2.9 psi = 204 g / cm² 2 = 20kPa (7) Slurry supply rate (pre-polishing): 150 mL / min (flow-through) Slurry supply rate (finishing polishing): 250 mL / min (flow-through) (8) Polishing time: 5 minutes

[0103] After polishing, the silicon wafer was cleaned in the same manner as in Example A, then the haze characteristics and Si polishing rate were measured, and surface defects (light point defects: LPDs) were measured using the following method. The results are shown in Table 2 below.

[0104] [Table 2]

[0105] [Measurement of surface defects] As with haze measurements, LPD was evaluated by measuring the LPD value in the dark-field composite grazing incidence channel (DCO) using a KLA Tencor Surfscan SP2 on cleaned silicon wafers. Pre-polished wafers were evaluated for sizes >250nm, and finish polished wafers for sizes >120nm.

[0106] Table 2 shows whether the polishing compositions of Examples 23, 25, and 27 showed improvement over the corresponding comparative examples (Comparative Examples 22, 24, and 26, respectively) for each characteristic. Specifically, for haze and LPD, an improvement can be evaluated if the value is lower than that of the corresponding comparative example, while for Si polishing speed, an improvement can be evaluated if the value is higher than that of the corresponding comparative example. As is clear from Table 2, by using the polishing compositions of the examples containing the additive components according to the present invention, it was possible to improve the polishing speed in both pre-polishing and finish polishing, even in the case of low-resistivity substrates, which are generally known to be difficult to chemically and mechanically polish, and in addition, the haze characteristics were improved and the formation of surface defects was reduced.

Claims

1. Abrasives, Basic components, At least one compound selected from the group consisting of quaternary polyammonium salts and quaternary ammonium salts having 6 or more carbon atoms, and Water-based carrier The quaternary ammonium salt having 6 or more carbon atoms is included in the following general formula (2): 【Chemistry 1】 It has, in the formula, R 7 , R 8 and R 9 R is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms or a benzyl group, 10 is a substituted or unsubstituted linear or branched alkyl group having 7 to 30 carbon atoms, Y - is the counterion, or Methyltriethylammonium ion, methyltripropylammonium ion, methyltributylammonium ion, methyltripentylammonium ion, methyltrihexylammonium ion, ethyltripropylammonium ion, ethyltributylammonium ion, ethyltripentylammonium ion, ethyltrihexylammonium ion, diethyldimethylammonium ion, propyltrimethylammonium ion, propyltriethylammonium ion, propyltributylammonium ion, propyltripentylammonium ion, propyltrihexylammonium ion, dipropyldimethylammonium ion, dipropyldiethylammonium ion, butyltrimethylammonium ion, butyltriethylammonium ion, butyltripropylammonium ion, butyltripentylammonium ion, butyltrihexylammonium ion, dibutyldimethylammonium ion, dibutyldiethylammonium ion, dibutyldipropylammonium ion, pentyltrimethylammonium ion, pel Having a cationic moiety selected from the group consisting of pentyltriethylammonium ion, pentyltripropylammonium ion, pentyltributylammonium ion, pentyltrihexylammonium ion, dipentyldimethylammonium ion, dipentyldiethylammonium ion, dipentyldipropylammonium ion, dipentyldibutylammonium ion, hexyltrimethylammonium ion, hexyltriethylammonium ion, hexyltripropylammonium ion, hexyltributylammonium ion, hexyltripentylammonium ion, dihexyldimethylammonium ion, dihexyldiethylammonium ion, dihexyldipropylammonium ion, dihexyldibutylammonium ion, dihexyldipentylammonium ion, benzylethyldimethylammonium ion, benzyltriethylammonium ion, benzyltripropylammonium ion, benzyltributylammonium ion, benzyltripentylammonium ion, and benzyltrihexylammonium ion, A chemical mechanical polishing composition having a pH of 7 to 12 (excluding those containing a benzotriazole derivative having at least one alkyl group).

2. The chemical mechanical polishing composition according to claim 1, wherein the at least one compound comprises a quaternary polyammonium salt and a quaternary ammonium salt having 6 or more carbon atoms.

3. The above at least one compound comprises a quaternary polyammonium salt, and the quaternary polyammonium salt is of the following general formula (1): 【Chemistry 2】 having, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R - are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, A is each independently a substituted or unsubstituted linear or branched alkylene group having 1 to 30 carbon atoms, n is an integer from 1 to 10, and X - is a counterion, the chemical mechanical polishing composition according to claim 1 or 2.

4. The chemical mechanical polishing composition according to claim 3, wherein the quaternary polyammonium salt is a quaternary diammonium salt, A in the general formula (1) is a substituted or unsubstituted linear or branched alkylene group having 1 to 15 carbon atoms, and n is 1.

5. The chemical mechanical polishing composition according to claim 1, wherein at least one of the compounds comprises a quaternary ammonium salt having 6 or more carbon atoms.

6. A chemical mechanical polishing composition according to any one of claims 1 to 5, further comprising an alkylated polymer having an amide structure.

7. A chemical mechanical polishing composition according to any one of claims 1 to 6, further comprising tetramethylammonium hydroxide.

8. A chemical mechanical polishing composition according to any one of claims 1 to 7, further comprising a water-soluble polymer different from an alkylated polymer having an amide structure.

9. The chemical mechanical polishing composition according to claim 8, wherein the water-soluble polymer comprises at least one selected from the group consisting of polyvinylpyrrolidone, polyvinylacetamide, cellulose derivatives, and polymers containing polyvinyl alcohol structural units.

10. At least one compound selected from the group consisting of quaternary polyammonium salts and quaternary ammonium salts having 6 or more carbon atoms, Water-based carriers, and A water-soluble polymer comprising at least one selected from the group consisting of polyvinylacetamide, cellulose derivatives, and polymers containing polyvinyl alcohol structural units in the main chain or side chain of the polymer. The quaternary ammonium salt having 6 or more carbon atoms is defined by the following general formula (2): 【Transformation 3】 It has, in the formula, R 7 , R 8 and R 9 R is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms or a benzyl group, 10 is a substituted or unsubstituted linear or branched alkyl group having 7 to 30 carbon atoms, Y - is the counterion, or Methyltriethylammonium ion, methyltripropylammonium ion, methyltributylammonium ion, methyltripentylammonium ion, methyltrihexylammonium ion, ethyltripropylammonium ion, ethyltributylammonium ion, ethyltripentylammonium ion, ethyltrihexylammonium ion, diethyldimethylammonium ion, propyltrimethylammonium ion, propyltriethylammonium ion, propyltributylammonium ion, propyltripentylammonium ion, propyltrihexylammonium ion, dipropyldimethylammonium ion, dipropyldiethylammonium ion, butyltrimethylammonium ion, butyltriethylammonium ion, butyltripropylammonium ion, butyltripentylammonium ion, butyltrihexylammonium ion, dibutyldimethylammonium ion, dibutyldiethylammonium ion, dibutyldipropylammonium ion, pentyltrimethylammonium ion, pentyltri A rinse composition having a cationic moiety selected from the group consisting of ammonium ion, pentyltripropylammonium ion, pentyltributylammonium ion, pentyltrihexylammonium ion, dipentyldimethylammonium ion, dipentyldiethylammonium ion, dipentyldipropylammonium ion, dipentyldibutylammonium ion, hexyltrimethylammonium ion, hexyltriethylammonium ion, hexyltripropylammonium ion, hexyltributylammonium ion, hexyltripentylammonium ion, dihexyldimethylammonium ion, dihexyldiethylammonium ion, dihexyldipropylammonium ion, dihexyldibutylammonium ion, dihexyldipentylammonium ion, benzylethyldimethylammonium ion, benzyltriethylammonium ion, benzyltripropylammonium ion, benzyltributylammonium ion, benzyltripentylammonium ion, and benzyltrihexylammonium ion (however,(Excluding those containing benzotriazole derivatives having at least one alkyl group.)

11. The rinse composition according to claim 10, wherein the at least one compound comprises a quaternary polyammonium salt and a quaternary ammonium salt having 6 or more carbon atoms.

12. The above at least one compound comprises a quaternary polyammonium salt, and the quaternary polyammonium salt is of the following general formula (1): 【Chemistry 4】 It has, in the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 A is independently a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, A is independently a substituted or unsubstituted linear or branched alkylene group having 1 to 30 carbon atoms, n is an integer from 1 to 10, and X - The rinse composition according to claim 10 or 11, wherein is a counterion.

13. The rinse composition according to claim 12, wherein the quaternary polyammonium salt is a quaternary diammonium salt, and A in the general formula (1) is a substituted or unsubstituted linear or branched alkylene group having 1 to 15 carbon atoms, and n is 1.

14. The rinse composition according to claim 10, wherein at least one of the compounds comprises a quaternary ammonium salt having 6 or more carbon atoms.

15. The rinse composition according to any one of claims 10 to 14, further comprising an alkylated polymer having an amide structure.

16. The rinse composition according to any one of claims 10 to 15, further comprising tetramethylammonium hydroxide.

17. A step of bringing a substrate into contact with a polishing pad and a chemical mechanical polishing composition according to any one of claims 1 to 9. The process of moving the polishing pad with respect to the substrate and the chemical mechanical polishing composition between them, and A step of polishing the substrate by wearing down at least a portion of it. A chemical mechanical polishing method for a substrate, including the method described above.

18. A step of bringing a substrate after chemical mechanical polishing into contact with a polishing pad and a rinse composition according to any one of claims 10 to 16, and The process of moving the polishing pad with the rinse composition between the substrate and the substrate. A method for rinsing a substrate, including [the specified element].

19. A method for chemical mechanical polishing of a substrate using a polishing apparatus comprising an upper platen and a lower platen, each to which a polishing pad is attached, and a carrier plate having at least one holding hole for holding the substrate, wherein The process involves holding the substrate in at least one holding hole of the carrier plate, and then sandwiching the carrier plate between the upper and lower plates to which polishing pads are attached, and A process of simultaneously polishing both sides of the substrate by rotating and revolving the carrier plate while supplying the chemical mechanical polishing composition according to any one of claims 1 to 9 to the polishing surface of the substrate. A chemical mechanical polishing method for a substrate, including the method described above.

20. A method for rinsing a substrate using a polishing apparatus comprising an upper platen and a lower platen, each having polishing pads attached to them, and a carrier plate having at least one holding hole for holding the substrate, A step of rotating and revolving the carrier plate while supplying the rinse composition according to any one of claims 10 to 16 to the polished surface of the substrate after chemical mechanical polishing. A method for rinsing a substrate, including [the specified element].

21. The chemical mechanical polishing composition according to claim 4, wherein the quaternary polyammonium salt is hexamethylenebis(trimethylammonium chloride).

22. The chemical mechanical polishing composition according to claim 5, wherein the quaternary ammonium salt having 6 or more carbon atoms has a cation portion of a methyltributylammonium ion.

23. The rinse composition according to claim 13, wherein the quaternary polyammonium salt is hexamethylenebis(trimethylammonium chloride).

24. The rinse composition according to claim 14, wherein the quaternary ammonium salt having 6 or more carbon atoms has a cation portion of a methyltributylammonium ion.

25. The chemical mechanical polishing composition according to claim 6, wherein the alkylated polymer having the amide structure is alkylated polyvinylpyrrolidone.

26. The rinse composition according to claim 15, wherein the alkylated polymer having the amide structure is alkylated polyvinylpyrrolidone.

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