CMP polishing solution, CMP polishing solution set and polishing method

Abstract

A polishing solution for CMP comprising abrasive particles, an additive, and water, wherein the abrasive particles comprise cerium-based particles, and the additive comprises (A1) a 4-pyrone compound represented by the following general formula (1) and (B) a compound having two or more nitrogen atoms bonded to a hydroxyalkyl group. A polishing solution for CMP comprising abrasive particles, an additive, and water, wherein the abrasive particles comprise cerium-based particles, and the additive comprises (A2) picolinic acid and (B) a compound having two or more nitrogen atoms bonded to a hydroxyalkyl group. [Chemical Formula 1] [In the formula, X11, X12, and X13 are each independently a hydrogen atom or a monovalent substituent.]

Description

Technology Field

[0001] The present disclosure relates to a polishing solution for CMP (chemical mechanical polishing), a set of polishing solutions for CMP, a polishing method, etc. Background Technology

[0002] In the semiconductor manufacturing field, as the performance of ultra-LSI devices increases, it has become difficult to achieve both high integration and high speed through miniaturization technology that is an extension of conventional technology. Therefore, technology that enables high integration in the vertical direction while advancing the miniaturization of semiconductor devices (i.e., technology that multilayers wiring) is being developed.

[0003] CMP technology is one of the most critical technologies in the process of manufacturing devices with multilayered wiring. CMP technology is a technique for planarizing the surface of a substrate obtained by forming a thin film on a substrate via chemical vapor deposition (CVD), etc. For example, planarization treatment by CMP is indispensable to secure the depth of focus in lithography. If there are irregularities on the substrate surface, problems arise, such as the inability to focus during the photolithography process or the inability to sufficiently form fine wiring structures. Furthermore, in the device manufacturing process, CMP technology includes a process for forming a device isolation (inter-device separation; STI: Shallow Trench Isolation) region by polishing a plasma oxide film (BPSG, HDP-SiO2, p-TEOS, etc.); and a process for forming an ILD film (an insulating film that electrically insulates metal components (wiring, etc.) within the same layer). It is also applied to processes such as flattening plugs (e.g., Al·Cu plugs) after embedding a film containing silicon oxide into metal wiring.

[0004] CMP is typically performed using a device capable of supplying a polishing liquid onto a polishing pad. Then, the surface of the gas is polished by supplying the polishing liquid between the surface of the gas and the polishing pad while pressing the gas against the polishing pad. As such, in CMP technology, the polishing liquid is one of the key technologies, and various polishing liquids have been developed to date in order to obtain high-performance polishing liquids (for example, see Patent Document 1 below).

[0005] Among the processes to which the CMP technology described above is applied, particularly in the CMP process of ILD films, it is necessary to polish silicon oxide at a high polishing rate. For this reason, in the CMP process of ILD films, silica-based polishing solutions (polishing solutions using abrasive particles containing silica-based particles) having a high polishing rate are mainly used (see, for example, Patent Document 2 below). However, with silica-based polishing solutions, it tends to be difficult to control polishing scratches, which are the cause of defects. Furthermore, with the recent miniaturization of wiring, it is desirable to minimize polishing scratches in the CMP process of ILD films as well; however, unlike the CMP process of insulating films for device isolation regions, mirror-finish polishing is generally not performed. Therefore, the use of cerium-based polishing solutions (polishing solutions using abrasive particles containing cerium-based particles), which have fewer polishing scratches compared to silica-based polishing solutions, is being considered (see, for example, Patent Document 3 below). Prior art literature

[0006] Japanese Published Patent Application No. 2008-288537, Japanese Published Patent Application No. Hei 9-316431, Japanese Published Patent Application No. Hei 10-102038 The problem to be solved

[0007] However, in cerium-based polishing solutions, it is difficult to achieve a high polishing rate of silicon oxide, and in particular, when polishing a pattern wafer having a fine uneven pattern consisting of convex parts (e.g., line parts) and concave parts (e.g., space parts), it is difficult to achieve a high polishing rate of silicon oxide in the convex parts.

[0008] One aspect of the present disclosure aims to provide a polishing solution for CMP capable of achieving a high polishing rate of silicon oxide on the convex portions in polishing a pattern wafer having a fine uneven pattern. Another aspect of the present disclosure aims to provide a set of polishing solutions for CMP for obtaining the polishing solution for CMP. Furthermore, another aspect of the present disclosure aims to provide a polishing method using the polishing solution for CMP or the set of polishing solutions for CMP. means of solving the problem

[0009] The present disclosure relates to the following [1] to

[17] , etc., in several aspects.

[0010] [1] A polishing solution for CMP containing abrasive particles, an additive, and water, wherein the abrasive particles contain cerium-based particles, and the additive comprises (A1) a 4-pyrone-based compound represented by the following general formula (1) and (B) a compound having two or more nitrogen atoms bonded to a hydroxyalkyl group.

[0011] [Chemical Formula 1]

[0012]

[0013] [During the meal, X 11 , X 12 and X 13 Each is independently a hydrogen atom or a monovalent substituent.

[0014] [2] A polishing solution for CMP described in [1], wherein the above (A1) component comprises at least one selected from the group consisting of 3-hydroxy-2-methyl-4-pyrone, 5-hydroxy-2-(hydroxymethyl)-4-pyrone, and 2-ethyl-3-hydroxy-4-pyrone.

[0015] [3] A polishing liquid for CMP described in [1] or [2], having a content of 0.01 to 5 mass% of the above (A1) component.

[0016] [4] A polishing solution for CMP described in any one of [1] to [3], wherein the above (B) component comprises ethylenedinitrilotetarethanol.

[0017] [5] A polishing solution for CMP described in any one of [1] to [4], wherein the above (B) component comprises ethylenedinitrilotetarpropanol.

[0018] [6] A polishing liquid for CMP described in any one of [1] to [5], wherein the content of the above (B) component is 0.001 to 5 mass%.

[0019] [7] A polishing solution for CMP described in any one of [1] to [6], wherein the above additive further comprises a saturated monocarboxylic acid.

[0020] [8] A polishing solution for CMP described in any one of [1] to [7], having a pH of 8.0 or less.

[0021] [9] A polishing solution for CMP containing abrasive particles, an additive, and water, wherein the abrasive particles contain cerium-based particles, and the additive contains (A2) picolinic acid and (B) a compound having two or more nitrogen atoms bonded to a hydroxyalkyl group.

[0022]

[10] A polishing liquid for CMP described in [9], having a content of 0.001 to 5 mass% of the above (A2) component.

[0023]

[11] A polishing solution for CMP described in [9] or

[10] , wherein the above (B) component comprises ethylenedinitrilotetarethanol.

[0024]

[12] A polishing solution for CMP described in any one of [9] to

[11] , wherein the above (B) component comprises ethylenedinitrilotetarpropanol.

[0025]

[13] A polishing liquid for CMP described in any one of [9] to

[12] , wherein the content of the above (B) component is 0.001 to 5 mass%.

[0026]

[14] A polishing solution for CMP described in any one of [9] to

[13] , having a pH of 8.0 or less.

[0027]

[15] A set of polishing liquids for CMP, wherein the components of the polishing liquid for CMP described in any one of [1] to

[14] are divided into a first liquid and a second liquid, the first liquid comprises the abrasive particles and water, and the second liquid comprises at least one of the additives and water.

[0028]

[16] A polishing method comprising a process of polishing a surface to be polished using a polishing liquid for CMP obtained by mixing the first liquid and the second liquid in a set of polishing liquids for CMP described in

[15] , or a polishing liquid for CMP described in any one of [1] to

[14] .

[0029]

[17] The polishing method described in

[16] , wherein the surface to be polished contains silicon oxide. Effects of the invention

[0030] According to one aspect of the present disclosure, a polishing solution for CMP can be provided that is capable of achieving a high polishing rate of silicon oxide on the convex portion in polishing a pattern wafer having a fine uneven pattern. Furthermore, according to another aspect of the present disclosure, a set of polishing solutions for CMP can be provided for obtaining the polishing solution for CMP. Furthermore, according to another aspect of the present disclosure, a polishing method using the polishing solution for CMP or the set of polishing solutions for CMP can be provided. Brief explanation of the drawing

[0031] Figure 1 is a schematic cross-sectional view showing the process of polishing an ILD film. Specific details for implementing the invention

[0032] Hereinafter, embodiments of the present disclosure will be described in detail.

[0033] In this specification, a numerical range indicated by "~" represents a range that includes the values ​​listed before and after "~" as the minimum and maximum values, respectively. "A or greater" in a numerical range means A and a range exceeding A. "A or less" in a numerical range means A and a range less than A. In numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in a given step may be arbitrarily combined with the upper or lower limit of a numerical range in another step. In numerical ranges described in this specification, the upper or lower limit of said numerical range may be substituted with the values ​​shown in the examples. "A or B" means that either A or B may be included, or both may be included. Unless otherwise specifically stated, the materials exemplified in this specification may be used as a single type or in combination of two or more types. The content of each component in the composition refers to the total amount of said multiple substances present in the composition, unless otherwise specifically stated, in cases where multiple substances corresponding to each component exist in the composition. The terms "layer" or "membrane" include, in addition to the structure formed on the entire surface when observed as a plan view, the structure formed on a part thereof. The term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, provided that the desired function of the process is achieved. The "hydroxyl group" does not include the OH structure found in carboxyl groups.

[0034] <CMP용 연마액>

[0035] The polishing solution for CMP according to the present embodiment (first embodiment and second embodiment; hereinafter the same) is a polishing solution for CMP containing abrasive particles, an additive, and water (hereinafter, depending on the case, simply referred to as "polishing solution"). The abrasive particles include cerium-based particles (particles containing a cerium-based compound). The additive of the polishing solution according to the first embodiment includes (A1) a 4-pyrone-based compound represented by the following general formula (1) (component (A1)) and (B) a compound having two or more nitrogen atoms bonded to a hydroxyalkyl group (component (B)). The additive of the polishing solution according to the second embodiment includes (A2) picolinic acid (component (A2)) and (B) a compound having two or more nitrogen atoms bonded to a hydroxyalkyl group (component (B)). The additive of the polishing solution according to the present embodiment may include component (A1), component (A2), and component (B).

[0036] [Chemical Formula 2]

[0037]

[0038] [During the meal, X 11 , X 12 and X 13 Each is independently a hydrogen atom or a monovalent substituent.

[0039] According to the polishing solution according to the present embodiment, a high polishing rate of silicon oxide in the convex portion can be achieved in polishing a pattern wafer having a fine uneven pattern composed of a convex portion (e.g., a Line portion) and a concave portion (e.g., a Space portion), and for example, a high polishing rate of silicon oxide in the convex portion can be achieved in polishing a region of Line / Space (L / S) = 30 μm / 570 μm in the pattern wafer. According to the polishing solution according to the present embodiment, in the evaluation method described in the example to be described later, a polishing rate of silicon oxide in the convex portion in a region of L / S = 30 μm / 570 μm can be obtained, for example, of 2100 nm / min or more.

[0040] Although the factors that enable achieving a high polishing rate of silicon oxide on the convex portion are not necessarily clear, it is presumed to be as follows. However, the factors are not limited to the following. That is, according to the polishing solution of the present embodiment, it is possible to obtain a high polishing rate of silicon oxide on the convex portion by increasing the interaction between the polishing solution and the silicon oxide on the convex portion through a synergistic effect caused by using component (A1) and component (B) together, or a synergistic effect caused by using component (A2) and component (B) together (for example, the chemical reaction between cerium-based particles in the polishing solution and silicon oxide on the convex portion (a reaction originating from the Si-O-Ce bond) is promoted), and a high polishing rate of silicon oxide on the convex portion can be achieved in polishing the L / S = 30 μm / 570 μm area of ​​the pattern wafer.

[0041] According to one embodiment of the polishing liquid according to the present embodiment, high-speed polishing of silicon oxide in a blanket wafer without an uneven pattern (for example, a polishing speed of 100 nm / min or more (preferably 250 nm / min or more, etc.)) can be achieved, while a high polishing speed of silicon oxide in the convex portion can be achieved in the polishing of the L / S = 30 μm / 570 μm area in a pattern wafer.

[0042] The polishing solution according to the present embodiment can be used for CMP of semiconductor wafer materials, for example, to polish a silicon oxide film provided on the surface of a semiconductor wafer. The polishing solution according to the present embodiment can be used in the CMP process of an ILD film.

[0043] (Georip)

[0044] The abrasive grains contain cerium-based particles. By using cerium-based particles as abrasive grains, it is easy to obtain a high polishing rate of silicon oxide on the convex portions of the pattern wafer while reducing polishing scratches occurring on the surface to be polished.

[0045] Examples of cerium-based compounds for cerium-based particles include cerium oxide, cerium hydroxide, cerium ammonium nitrate, cerium acetate, cerium sulfate hydrate, cerium bromide, cerium chloride, cerium oxalate, cerium nitrate, and cerium carbonate. Cerium-based particles may contain cerium oxide from the perspective that a high polishing rate of silicon oxide can be easily obtained in the convex portion of a pattern wafer (convex portion in the L / S = 30 μm / 570 μm region, etc.; hereinafter the same). By using cerium-based particles containing cerium oxide (cerium oxide particles), it is easy to achieve a high polishing rate of silicon oxide in the convex portion of a pattern wafer, and at the same time, a polished surface with few polishing scratches and excellent flatness can be easily obtained.

[0046] The cerium oxide particles may include polycrystalline cerium oxide having grain boundaries. Such polycrystalline cerium oxide particles have the property of becoming finer during polishing while simultaneously having active surfaces appearing one after another, and can maintain a high polishing rate of silicon oxide on the convex portion of the pattern wafer.

[0047] Methods for manufacturing cerium oxide particles include calcination; oxidation with hydrogen peroxide, etc. When calcining, the temperature during calcination may be 350 to 900°C. If the manufactured cerium oxide particles are aggregated, the particles may be mechanically ground. As for the grinding method, dry grinding with a jet mill, etc., or wet grinding with a planetary bead mill, etc. For example, the jet mill described in "Journal of Chemical Engineering," Vol. 6, No. 5, (1980), pp. 527 to 532 may be used.

[0048] The zeta potential (surface potential) of the abrasive grains in the polishing solution may be positive (the zeta potential may exceed 0 mV) from the perspective that a high polishing rate of silicon oxide on the convex portion of the pattern wafer is easily obtained. The zeta potential of the abrasive grains can be measured, for example, using a dynamic light scattering zeta potential measuring device (e.g., manufactured by Beckmann Coulter Corp., trade name: DelsaNano C). The zeta potential of the abrasive grains can be adjusted using additives. For example, by contacting the abrasive grains with an acid component (e.g., acetic acid), abrasive grains having a positive zeta potential can be obtained.

[0049] The average particle size of the abrasive grain may be 50 nm or more, 70 nm or more, 100 nm or more, greater than 100 nm, 105 nm or more, 110 nm or more, 115 nm or more, 120 nm or more, 125 nm or more, 130 nm or more, 135 nm or more, or 140 nm or more, from the perspective of easily obtaining a high polishing rate of silicon oxide in the convex portion of the pattern wafer. The average particle size of the abrasive grain may be 500 nm or less, 300 nm or less, 200 nm or less, 180 nm or less, 150 nm or less, or 140 nm or less, from the perspective of easily suppressing the occurrence of polishing scratches. From these perspectives, the average particle size of the abrasive grains may be 50–500 nm, 50–200 nm, 50–150 nm, 70–500 nm, 70–200 nm, 70–150 nm, 100–500 nm, 100–200 nm, or 100–150 nm. By adjusting the average particle size of the abrasive grains, high polishing speed and low scratch characteristics of silicon oxide according to the average particle size of the abrasive grains are efficiently obtained.

[0050] "Average particle size of abrasives" refers to the median value of the volume distribution measured by a laser diffraction-scattering particle size distribution measuring device for a sample of a slurry in which abrasives are dispersed, and can be measured using a Microtrac MT3300EXII manufactured by MicrotracBEL Corp., etc. For example, a sample is prepared by adjusting the abrasive content by dispersing abrasives in water so that the abrasive content is 0.25 mass% based on the total mass of the sample, and this sample is set up in the measuring device to measure the median value of the volume distribution. When measuring the particle size of abrasives in a polishing solution, a sample is prepared by adjusting the abrasive content in the polishing solution so that the abrasive content is 0.25 mass% based on the total mass of the sample, and this sample can be measured by the same method.

[0051] The content of abrasive particles may be within the following ranges based on the total mass of the polishing solution, in order to provide an excellent balance between the polishing rate of silicon oxide and the dispersion stability of the abrasive particles in the convex portion of the pattern wafer. The content of abrasive particles may be 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, 0.15 mass% or more, 0.2 mass% or more, 0.25 mass% or more, 0.3 mass% or more, 0.5 mass% or more, 0.8 mass% or more, or 1 mass% or more. The content of abrasive particles may be 10 mass% or less, 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.8 mass% or less, 0.5 mass% or less, 0.3 mass% or less, or 0.25 mass% or less. In these regards, the content of the abrasives may be 0.01 to 10 mass%, 0.01 to 2 mass%, 0.01 to 1 mass%, 0.01 to 0.5 mass%, 0.1 to 10 mass%, 0.1 to 2 mass%, 0.1 to 1 mass%, 0.1 to 0.5 mass%, 0.5 to 10 mass%, 0.5 to 2 mass%, or 0.5 to 1 mass%.

[0052] (Additives)

[0053] [(A1) Components: 4-pyronic compounds]

[0054] The additive of the polishing liquid according to the first embodiment includes a 4-pyrone compound represented by general formula (1) as a component (A1) (hereinafter, depending on the case, simply referred to as a "4-pyrone compound"). It is presumed that by using a 4-pyrone compound, the interaction between the polishing liquid and silicon oxide increases, thereby making it easier to increase the polishing speed. Furthermore, although the 4-pyrone compound is an additive capable of greatly increasing the interaction between the polishing liquid and silicon oxide, it is thought that it can suppress the aggregation of abrasive particles because it does not have the effect of weakening repulsive forces, such as electrostatic repulsion between abrasive particles.

[0055] A 4-pyrone compound is a compound represented by the following general formula (1), and is a compound having a structure in which a hydroxyl group is bonded to a carbon atom adjacent to a carbon atom of a carbonyl group. A "4-pyrone compound" is a heterocyclic compound having a γ-pyrone ring (6-membered ring) having an oxy group and a carbonyl group, with the carbonyl group positioned at the 4th position relative to the oxy group. In a 4-pyrone compound, a hydroxyl group is bonded to a carbon atom adjacent to a carboxyl group in this γ-pyrone ring, and other carbon atoms may be substituted with substituents other than hydrogen atoms.

[0056] [Chemical Formula 3]

[0057]

[0058] During the meal, X 11 , X 12 and X 13Each is independently a hydrogen atom or a monovalent substituent. Examples of monovalent substituents include aldehyde groups, hydroxyl groups, carboxyl groups, carboxylic acid bases, sulfonic acid groups, phosphate groups, bromine atoms, chlorine atoms, iodine atoms, fluorine atoms, nitro groups, hydrazine groups, alkyl groups (e.g., C1-C8 alkyl groups), aryl groups (e.g., C6-C2 aryl groups), alkenyl groups (e.g., C1-C8 alkenyl groups), etc. Alkyl groups, aryl groups, and alkenyl groups may be substituted with OH, COOH, Br, Cl, I, NO2, etc. X 11 , X 12 and X 13 As, in the case where it has a monovalent substituent, the substituent may be bonded to a carbon atom adjacent to the oxy group, i.e., X 11 and X 12 g can be a substitution. X 11 , X 12 and X 13 At least two of them may be hydrogen atoms.

[0059] The 4-pyrone compound may include at least one selected from the group consisting of 3-hydroxy-2-methyl-4-pyrone (alias: 3-hydroxy-2-methyl-4H-pyran-4-one, maltol), 5-hydroxy-2-(hydroxymethyl)-4-pyrone (alias: 5-hydroxy-2-(hydroxymethyl)-4H-pyran-4-one, uric acid), and 2-ethyl-3-hydroxy-4-pyrone (alias: 2-ethyl-3-hydroxy-4H-pyran-4-one), and may include 3-hydroxy-2-methyl-4-pyrone. The 4-pyrone compound may be used as a single type or in combination of two or more types.

[0060] The 4-pyrone-based compound may be water-soluble. By using a compound with high solubility in water, a desired amount of additive can be effectively dissolved in the polishing solution, and the effects of improving polishing speed and suppressing aggregation of abrasive particles can be achieved at an even higher level. The solubility of the 4-pyrone-based compound in 100g of water at room temperature (25℃) may be 0.001g or more, 0.005g or more, 0.01g or more, or 0.05g or more. There is no particular upper limit for solubility.

[0061] The content of the 4-pyrone compound may be in the following range based on the total mass of the polishing solution, from the perspective of easily obtaining a high polishing rate of silicon oxide in the convex portion of the pattern wafer and from the perspective of easily achieving high-speed polishing of silicon oxide in the blanket wafer. The content of 4-pyrone compounds may be 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.015 mass% or more, 0.02 mass% or more, 0.025 mass% or more, 0.03 mass% or more, 0.032 mass% or more, 0.034 mass% or more, 0.035 mass% or more, 0.04 mass% or more, 0.05 mass% or more, 0.08 mass% or more, 0.1 mass% or more, 0.13 mass% or more, 0.15 mass% or more, 0.18 mass% or more, or 0.2 mass% or more. The content of 4-pyrone compounds may be 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.8 mass% or less, 0.5 mass% or less, 0.3 mass% or less, 0.2 mass% or less, 0.18 mass% or less, 0.15 mass% or less, 0.13 mass% or less, 0.1 mass% or less, 0.08 mass% or less, 0.05 mass% or less, 0.04 mass% or less, 0.035 mass% or less, or 0.034 mass% or less. In these regards, the content of the 4-pyrone compound may be 0.001 to 5 mass%, 0.001 to 1 mass%, 0.001 to 0.3 mass%, 0.001 to 0.1 mass%, 0.001 to 0.05 mass%, 0.01 to 5 mass%, 0.01 to 1 mass%, 0.01 to 0.3 mass%, 0.01 to 0.1 mass%, 0.01 to 0.05 mass%, 0.02 to 5 mass%, 0.02 to 1 mass%, 0.02 to 0.3 mass%, 0.02 to 0.1 mass%, or 0.02 to 0.05 mass%.

[0062] The mass ratio A1 (4-pyrone compound / abrasive grain) of the content of the 4-pyrone compound to the content of the abrasive grain may be within the following ranges from the perspective of making it easier to obtain a high polishing rate of silicon oxide in the convex portion of the pattern wafer. The mass ratio A1 may be 0.01 or more, 0.03 or more, 0.5 or more, 0.08 or more, 0.1 or more, 0.12 or more, 0.13 or more, 0.15 or more, 0.18 or more, or 0.2 or more. The mass ratio A1 may be 1 or less, less than 1, 0.8 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.2 or less, 0.18 or less, 0.15 or less, 0.13 or less, 0.12 or less, or 0.1 or less. From these perspectives, the mass ratio A1 may be 0.01~1, 0.01~0.3, 0.01~0.15, 0.1~1, 0.1~0.3, 0.1~0.15, 0.12~1, 0.12~0.3, or 0.12~0.15.

[0063] [(A2) Component: Picolinic acid]

[0064] The additive of the polishing liquid according to the second embodiment includes picolinic acid as the (A2) component. It is presumed that by using the (A2) component, the interaction between the polishing liquid and silicon oxide increases, thereby making it easier to increase the polishing speed.

[0065] The content of picolinic acid may be within the following ranges based on the total mass of the polishing solution, from the perspective of easily obtaining a high polishing rate of silicon oxide in the convex portion of the pattern wafer. The content of picolinic acid may be 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.03 mass% or more, 0.05 mass% or more, 0.08 mass% or more, 0.1 mass% or more, 0.12 mass% or more, 0.15 mass% or more, 0.18 mass% or more, or 0.2 mass% or more. The content of picolinic acid may be 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.8 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, or 0.2 mass% or less. In these regards, the content of picolinic acid may be 0.001 to 5 mass%, 0.001 to 1 mass%, 0.001 to 0.5 mass%, 0.001 to 0.3 mass%, 0.01 to 5 mass%, 0.01 to 1 mass%, 0.01 to 0.5 mass%, 0.01 to 0.3 mass%, 0.1 to 5 mass%, 0.1 to 1 mass%, 0.1 to 0.5 mass%, or 0.1 to 0.3 mass%.

[0066] The mass ratio A2 (picolinic acid / abrasive particles) of picolinic acid content to abrasive particle content may be within the following ranges from the perspective of making it easier to obtain a high polishing rate of silicon oxide in the convex portion of the pattern wafer. The mass ratio A2 may be 0.01 or more, 0.03 or more, 0.05 or more, 0.08 or more, 0.1 or more, 0.12 or more, 0.15 or more, 0.18 or more, or 0.2 or more. The mass ratio A2 may be 1 or less, less than 1, 0.8 or less, 0.6 or less, 0.5 or less, 0.4 or less, 0.3 or less, 0.25 or less, or 0.2 or less. In these regard, the mass ratio A2 may be 0.01~1, 0.01~0.5, 0.01~0.3, 0.01~0.2, 0.05~1, 0.05~0.5, 0.05~0.3, 0.05~0.2, 0.1~1, 0.1~0.5, 0.1~0.3, or 0.1~0.2.

[0067] [(B) Component: Nitrogen-containing hydroxyalkyl compound]

[0068] The additive of the polishing liquid according to the present embodiment comprises, as component (B), a compound having two or more nitrogen atoms to which a hydroxyalkyl group is bonded (a nitrogen-containing hydroxyalkyl compound). In component (B), a hydroxyalkyl group is directly bonded to a nitrogen atom, and a hydroxyl group is directly bonded to the alkyl group directly bonded to the nitrogen atom. As the hydroxyalkyl group bonded to the nitrogen atom, component (B) may use an alkyl group that does not have a substituent other than a hydroxyl group.

[0069] (B) The component may include a compound having a nitrogen atom bonded to two hydroxyalkyl groups, and may include a compound having two or more nitrogen atoms bonded to two hydroxyalkyl groups, in order to easily obtain a high polishing rate of silicon oxide in the convex portion of the pattern wafer.

[0070] (B) The number of nitrogen atoms in one molecule of component (B) may be 2 to 5, 2 to 4, or 2 to 3, from the perspective of easily obtaining a high polishing rate of silicon oxide in the convex portion of the pattern wafer. (B) The number of hydroxyl groups in one molecule of component (B) may be 2 to 6, 2 to 5, 2 to 4, 3 to 6, 3 to 5, 3 to 4, 4 to 6, or 4 to 5, from the perspective of easily obtaining a high polishing rate of silicon oxide in the convex portion of the pattern wafer.

[0071] (B) The component may have a hydroxyalkyl group having 1 to 4, 2 to 4, 3 to 4, 1 to 3, 2 to 3, or 1 to 2 carbon atoms bonded to a nitrogen atom, in order to easily obtain a high polishing rate of silicon oxide in the convex portion of the pattern wafer. (B) The component may have a hydroxyalkyl group having 1 to 3 or 1 to 2 hydroxyalkyl groups bonded to a nitrogen atom, in order to easily obtain a high polishing rate of silicon oxide in the convex portion of the pattern wafer.

[0072] (B) In order to obtain a high polishing rate of silicon oxide in the convex portion of the pattern wafer, the component may have an alkylene group between two nitrogen atoms bonded to a hydroxyalkyl group, and the number of carbon atoms in the alkylene group may be 1 to 4, 2 to 4, 1 to 3, 2 to 3, or 1 to 2.

[0073] (B) The component may include a compound represented by the following general formula (I) in order to easily obtain a high polishing rate of silicon oxide in the convex portion of the pattern wafer.

[0074] [Chemical Formula 4]

[0075]

[0076] [In the expression, n is an integer greater than or equal to 1, and R 11 , R 12 , R 13 and R 14 Each independently represents a hydrogen atom or an organic group, and R 11 and R 12 One or both are hydroxyalkyl groups, and R 13 and R 14 One or both are hydroxyalkyl groups.

[0077] n is the number of carbon atoms in the alkylene group between the two nitrogen atoms to which the hydroxyalkyl group is bonded, and may be within the range specified above. The organic group may be a substituted or unsubstituted alkyl group, a hydroxyalkyl group, or a group having a nitrogen atom to which a hydroxyalkyl group is bonded. Examples of substituents for the alkyl group include hydroxyl groups, carboxyl groups, amino groups, sulfo groups, nitro groups, etc. R 11 , R 12 , R 13 or R 14 In the case where it is a hydroxyalkyl group, the number of carbon atoms of the hydroxyalkyl group may be within the range described above as the number of carbon atoms of the hydroxyalkyl group bonded to the nitrogen atom.

[0078] (B) Examples of components include ethylenedinitrillotetraethanol (THEED: 2,2',2'',2'''-ethylenedinitrillotetraethanol (alias: N,N,N',N'-Tetrakis(2-hydroxyethyl)ethylenediamine) etc.), ethylenedinitrillotetrapropanol (EDTP: 1,1',1'',1'''-ethylenedinitrillotetra-2-propanol (alias: N,N,N',N'-Tetrakis(2-hydroxypropyl)ethylenediamine) etc.), N,N,N',N'',N''-pentakis(2-hydroxypropyl)diethylenetriamine, etc. (B) The component may include at least one selected from the group consisting of ethylenedinitrilotetarethanol and ethylenedinitrilotetarpropanol, from the view that a high polishing rate of silicon oxide in the convex portion of the pattern wafer is easy to obtain, and high-speed polishing of silicon oxide in the blanket wafer is easy to achieve, and may include ethylenedinitrilotetarethanol and ethylenedinitrilotetarpropanol. (B) The component may include a compound that does not have a carboxyl group from the view that a high polishing rate of silicon oxide in the convex portion of the pattern wafer is easy to obtain.

[0079] (B) The molecular weight of the component may be in the following ranges from the perspective of easily obtaining a high polishing rate of silicon oxide in the convex portion of the pattern wafer. (B) The molecular weight of the component may be 50 or more, 60 or more, 70 or more, 80 or more, 85 or more, 90 or more, 100 or more, 110 or more, 120 or more, 123 or more, 125 or more, 130 or more, 140 or more, 148 or more, 150 or more, 160 or more, 170 or more, 180 or more, 200 or more, 210 or more, 230 or more, 250 or more, greater than 250, or greater than 280. (B) The molecular weight of the component may be 1000 or less, less than 1000, 900 or less, 800 or less, 700 or less, 600 or less, 500 or less, 400 or less, 350 or less, 300 or less, 280 or less, 250 or less, less than 250, or 240 or less. In this regard, the molecular weight of the component (B) may be 50~1000, 50~500, 50~300, 50~250, 200~1000, 200~500, 200~300, 200~250, 250~1000, 250~500, or 250~300.

[0080] In the polishing solution according to the first embodiment, regarding the content of component (B), the content of ethylenedinitrilotetarethanol, or the content of ethylenedinitrilotetarpropanol, the content B1 may be in the following range based on the total mass of the polishing solution, from the view that a high polishing rate of silicon oxide in the convex portion of the pattern wafer is easily obtained. The content B1 may be 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.015 mass% or more, 0.02 mass% or more, 0.025 mass% or more, 0.03 mass% or more, 0.035 mass% or more, 0.04 mass% or more, 0.045 mass% or more, or 0.05 mass% or more. The content of B1 may be 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, 0.2 mass% or less, 0.15 mass% or less, 0.1 mass% or less, 0.08 mass% or less, 0.06 mass% or less, 0.05 mass% or less, 0.045 mass% or less, 0.04 mass% or less, 0.035 mass% or less, 0.03 mass% or less, 0.025 mass% or less, or 0.02 mass% or less. In these regards, the content B1 may be 0.001 to 5 mass%, 0.001 to 1 mass%, 0.001 to 0.1 mass%, 0.001 to 0.05 mass%, 0.01 to 5 mass%, 0.01 to 1 mass%, 0.01 to 0.1 mass%, 0.01 to 0.05 mass%, 0.02 to 5 mass%, 0.02 to 1 mass%, 0.02 to 0.1 mass%, or 0.02 to 0.05 mass%.

[0081] In the polishing solution according to the second embodiment, the content of component (B), the content of ethylenedinitrilotetarethanol, or the content of ethylenedinitrilotetarpropanol, wherein the content B2 may be within the following range based on the total mass of the polishing solution, from the perspective of easily obtaining a high polishing rate of silicon oxide in the convex portion of the pattern wafer and from the perspective of easily achieving high-speed polishing of silicon oxide in the blanket wafer. Content B2 may be 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.015 mass% or more, 0.02 mass% or more, 0.025 mass% or more, 0.03 mass% or more, 0.035 mass% or more, 0.04 mass% or more, 0.045 mass% or more, 0.05 mass% or more, 0.06 mass% or more, 0.08 mass% or more, 0.1 mass% or more, 0.12 mass% or more, 0.13 mass% or more, 0.15 mass% or more, 0.2 mass% or more, or 0.22 mass% or more. The content of B2 may be 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, 0.22 mass% or less, 0.2 mass% or less, 0.15 mass% or less, 0.13 mass% or less, 0.12 mass% or less, 0.1 mass% or less, 0.08 mass% or less, 0.06 mass% or less, 0.05 mass% or less, 0.045 mass% or less, 0.04 mass% or less, 0.035 mass% or less, 0.03 mass% or less, 0.025 mass% or less, 0.02 mass% or less, 0.015 mass% or less, or 0.01 mass% or less. In these regards, the content B2 may be 0.001 to 5 mass%, 0.001 to 1 mass%, 0.001 to 0.3 mass%, 0.001 to 0.05 mass%, 0.01 to 5 mass%, 0.01 to 1 mass%, 0.01 to 0.3 mass%, 0.01 to 0.05 mass%, 0.02 to 5 mass%, 0.02 to 1 mass%, 0.02 to 0.3 mass%, or 0.02 to 0.05 mass%.

[0082] In the polishing solution according to the first embodiment, the mass ratio of the content of component (B) to the content of abrasive particles (component (B) / abrasive particles), the mass ratio of the content of ethylene dynitrilotetarethanol to the content of abrasive particles (ethylene dynitrilotetarethanol / abrasive particles), or the mass ratio of the content of ethylene dynitrilotetarpropanol to the content of abrasive particles (ethylene dynitrilotetarpropanol / abrasive particles), wherein the mass ratio B11 may be in the following range from the perspective of easily obtaining a high polishing rate of silicon oxide in the convex portion of the pattern wafer. The mass ratio B11 may be 0.001 or more, 0.005 or more, 0.01 or more, 0.02 or more, 0.03 or more, 0.05 or more, 0.08 or more, 0.1 or more, 0.12 or more, 0.15 or more, 0.18 or more, or 0.2 or more. The mass ratio B11 may be 10 or less, 5 or less, 2 or less, 1 or less, less than 1, 0.5 or less, 0.3 or less, 0.2 or less, 0.18 or less, 0.15 or less, 0.12 or less, 0.1 or less, 0.08 or less, 0.05 or less, 0.03 or less, or 0.02 or less. In these regards, the mass ratio B11 may be 0.001 to 10, 0.001 to 1, 0.001 to 0.3, 0.001 to 0.1, 0.01 to 10, 0.01 to 1, 0.01 to 0.3, 0.01 to 0.1, 0.02 to 10, 0.02 to 1, 0.02 to 0.3, or 0.02 to 0.1.

[0083] In the polishing solution according to the second embodiment, the mass ratio of the content of component (B) to the content of abrasive particles (component (B) / abrasive particles), the mass ratio of the content of ethylene dynitrilotetarethanol to the content of abrasive particles (ethylene dynitrilotetarethanol / abrasive particles), or the mass ratio of the content of ethylene dynitrilotetarpropanol to the content of abrasive particles (ethylene dynitrilotetarpropanol / abrasive particles), wherein the mass ratio B21 may be within the following range from the perspective of easily obtaining a high polishing rate of silicon oxide in the convex portion of the pattern wafer. The mass ratio B21 may be 0.001 or more, 0.005 or more, 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, 0.05 or more, 0.06 or more, 0.08 or more, 0.1 or more, 0.13 or more, 0.15 or more, 0.2 or more, or 0.22 or more. The mass ratio B21 may be 10 or less, 5 or less, 2 or less, 1 or less, less than 1, 0.5 or less, 0.3 or less, 0.25 or less, 0.22 or less, 0.2 or less, 0.15 or less, 0.13 or less, 0.1 or less, 0.08 or less, 0.06 or less, 0.05 or less, 0.04 or less, 0.03 or less, 0.02 or less, or 0.01 or less. In these regard, the mass ratio B21 may be 0.001~10, 0.001~1, 0.001~0.3, 0.001~0.2, 0.01~10, 0.01~1, 0.01~0.3, 0.01~0.2, 0.03~10, 0.03~1, 0.03~0.3, or 0.03~0.2.

[0084] In the polishing solution according to the first embodiment, the mass ratio of the content of component (B) to the content of component (A1) (component (B) / component (A1)), the mass ratio of the content of ethylenedinitrilotetetarethanol to the content of component (A1) (ethylenedinitrilotetarethanol / component (A1)), or the mass ratio of the content of ethylenedinitrilotetarpropanol to the content of component (A1) (ethylenedinitrilotetarpropanol / component (A1)), wherein the mass ratio B12 may be within the following range from the perspective of easily obtaining a high polishing rate of silicon oxide in the convex portion of the pattern wafer. The mass ratio B12 may be 0.01 or more, 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.3 or more, 0.5 or more, 0.6 or more, 0.8 or more, 0.85 or more, 0.9 or more, 1 or more, greater than 1, 1.1 or more, 1.2 or more, or 1.4 or more. The mass ratio B12 may be 10 or less, 8 or less, 5 or less, 2 or less, 1.5 or less, 1.4 or less, 1.2 or less, 1.1 or less, 1 or less, less than 1, 0.9 or less, 0.85 or less, 0.8 or less, 0.6 or less, 0.5 or less, 0.3 or less, 0.2 or less, 0.15 or less, or 0.1 or less. In these regard, the mass ratio B12 may be 0.01~10, 0.01~2, 0.01~1, 0.01~0.5, 0.05~10, 0.05~2, 0.05~1, 0.05~0.5, 0.15~10, 0.15~2, 0.15~1, or 0.15~0.5.

[0085] In the polishing solution according to the second embodiment, the mass ratio of the content of component (B) to the content of component (A2) (component (B) / component (A2)), the mass ratio of the content of ethylenedinitrilotetetarethanol to the content of component (A2) (ethylenedinitrilotetarethanol / component (A2)), or the mass ratio of the content of ethylenedinitrilotetarpropanol to the content of component (A2) (ethylenedinitrilotetarpropanol / component (A2)), wherein the mass ratio B22 may be within the following range from the perspective of easily obtaining a high polishing rate of silicon oxide in the convex portion of the pattern wafer. The mass ratio B22 may be 0.01 or more, 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0.3 or more, 0.5 or more, 0.6 or more, 0.65 or more, 0.7 or more, 0.8 or more, 1 or more, greater than 1, or 1.1 or more. The mass ratio B22 may be 10 or less, 8 or less, 5 or less, 2 or less, 1.5 or less, 1.2 or less, 1.1 or less, 1 or less, less than 1, 0.8 or less, 0.7 or less, 0.65 or less, 0.6 or less, 0.5 or less, 0.3 or less, 0.25 or less, 0.2 or less, 0.15 or less, 0.1 or less, or 0.05 or less. In these regard, the mass ratio B22 may be 0.01 to 10, 0.01 to 2, 0.01 to 1, 0.01 to 0.8, 0.1 to 10, 0.1 to 2, 0.1 to 1, 0.1 to 0.8, 0.2 to 10, 0.2 to 2, 0.2 to 1, or 0.2 to 0.8.

[0086] [Saturated monocarboxylic acid]

[0087] The additive of the polishing solution according to the present embodiment may include a saturated monocarboxylic acid. By using a saturated monocarboxylic acid, it is easy to obtain a sufficiently small polishing speed of silicon nitride that can be used as a stopper material, and at the same time, the dispersibility of cerium-based particles is improved, and the advantage is obtained that the in-plane uniformity, which is an indicator of non-uniformity within the polishing surface of the polishing speed, can be improved without lowering the polishing speed of the pattern wafer (e.g., a semiconductor substrate having an uneven pattern).

[0088] Examples of saturated monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hydroangelic acid, capronic acid, 2-methylpenteic acid, 4-methylpenteic acid, 2,3-dimethylbuteic acid, 2-ethylbuteic acid, 2,2-dimethylbuteic acid, 3,3-dimethylbuteic acid, etc. Saturated monocarboxylic acids may include aliphatic carboxylic acids from the viewpoint that the aforementioned additive effect of saturated monocarboxylic acids is easily obtained. Saturated monocarboxylic acids may include saturated monocarboxylic acids having 2 to 6 carbon atoms from the viewpoint that the effect of suppressing the polishing speed of silicon nitride is effectively obtained, and the effect of improving uniformity within the plane is obtained more favorably, and may include at least one selected from the group consisting of acetic acid and propionic acid.

[0089] The content of saturated monocarboxylic acid (e.g., saturated monocarboxylic acid having 2 to 6 carbon atoms) may be in the following range based on the total mass of the polishing solution, in order to effectively obtain the effect of improving in-plane uniformity, the effect of improving the polishing speed of the pattern wafer, and the effect of suppressing the polishing speed of silicon nitride. The content of saturated monocarboxylic acid may be 0.0001 mass% or more, 0.0005 mass% or more, 0.001 mass% or more, 0.002 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.02 mass% or more, 0.03 mass% or more, 0.04 mass% or more, or 0.045 mass% or more. The content of saturated monocarboxylic acid may be 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, 0.2 mass% or less, 0.1 mass% or less, 0.05 mass% or less, or 0.045 mass% or less. In these regards, the content of saturated monocarboxylic acid may be 0.0001 to 5 mass%, 0.0001 to 1 mass%, 0.0001 to 0.1 mass%, 0.0001 to 0.05 mass%, 0.01 to 5 mass%, 0.01 to 1 mass%, 0.01 to 0.1 mass%, 0.01 to 0.05 mass%, 0.03 to 5 mass%, 0.03 to 1 mass%, 0.03 to 0.1 mass%, or 0.03 to 0.05 mass%. The content of saturated monocarboxylic acid may be 0.04 mass% or less, 0.03 mass% or less, 0.02 mass% or less, 0.01 mass% or less, 0.005 mass% or less, 0.002 mass% or less, 0.001 mass% or less, 0.0005 mass% or less, or substantially 0 mass%.

[0090] [Other additives]

[0091] The additive of the polishing solution according to the present embodiment may further include other components (components not corresponding to each component described above) depending on the desired characteristics. Examples of such components include nonionic polymers; cationic compounds; pH adjusters described later; polar solvents such as ethanol and acetone; and cyclic monocarboxylic acids.

[0092] The polishing solution according to the present embodiment may contain compound a having a molecular weight of 100,000 or less and having four or more hydroxyl groups, or it may not contain compound a. The polishing solution according to the present embodiment may contain compound b having four or more amino groups, or it may not contain compound b. The content of compound b may be 0.001 mass% or less, less than 0.001 mass%, 0.0001 mass% or less, 0.00001 mass% or less, or substantially 0 mass% based on the total mass of the polishing solution. The mass ratio of the content of compound a to the content of compound b (compound a / compound b) may be 0.10 or less, or less than 0.10.

[0093] (water)

[0094] Water may include at least one type selected from the group consisting of deionized water, ion-exchanged water, and ultrapure water, although not specifically limited.

[0095] (pH)

[0096] The pH of the polishing solution according to the present embodiment may be within the following range. The pH is 12.0 or less, 11.0 or less, 10.5 or less, less than 10.5, 10.0 or less, less than 10.0, less than 10.0, 9.5 or less, 9.0 or less, less than 9.0, less than 8.5 or less, 8.0 or less, less than 8.0, less than 7.5 or less, 7.3 or less, 7.0 or less, less than 7.0, 6.5 or less, 6.0 or less, less than 6.0, 5.6 or less, 5.5 or less, less than 5.5, 5.1 or less, 5.0 or less, 4.8 or less, 4.7 or less, 4.6 or less, 4.5 or less, 4.4. It may be 4.3 or less, 4.2 or less, 4.1 or less, or 4.0 or less. The pH may be 3.0 or higher, 3.5 or higher, 3.7 or higher, 3.8 or higher, 4.0 or higher, greater than 4.0, 4.1 or higher, 4.2 or higher, 4.3 or higher, 4.4 or higher, 4.5 or higher, 4.6 or higher, 4.7 or higher, 4.8 or higher, 4.0 or higher, greater than 4.0, 4.1 or higher, 4.2 or higher, 4.3 or higher, 4.4 or higher, 4.5 or higher, 4.6 or higher, 4.7 or higher, 4.8 or higher, 5.0 or higher, 5.1 or higher, 5.5 or higher, greater than 5.5, 5.6 or higher, 6.0 or higher, greater than 6.0, 6.5 or higher, 7.0 or higher, greater than 7.0, or 7.3 or higher. In these respects, pH may be 3.0 to 12.0, 3.0 or more and less than 9.0, 3.0 to 8.0, 3.0 to 5.5, 3.0 to 5.0, 3.5 to 12.0, 3.5 or more and less than 9.0, 3.5 to 8.0, 3.5 to 5.5, 3.5 to 5.0, 4.0 to 12.0, 4.0 or more and less than 9.0, 4.0 to 8.0, 4.0 to 5.5, or 4.0 to 5.0.pH can be measured by the method described in the examples.

[0097] Since pH can change depending on the type of compound used as an additive, a pH adjuster may be used to adjust the pH to the above range. There are no particular restrictions on the pH adjuster, but examples include acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and boric acid; and bases such as sodium hydroxide, ammonia (e.g., water of ammonia), potassium hydroxide, and calcium hydroxide. The aforementioned additives, such as saturated monocarboxylic acids, may also be used for pH adjustment. From the perspective of improving productivity, a polishing solution may be prepared without using a pH adjuster, and this polishing solution may be applied directly to CMP.

[0098] Preparation and Usage Method of Polishing Solution

[0099] The polishing solution according to the present embodiment can be classified into (a) a standard type, (b) a concentrated type, and (c) a multi-liquid type (e.g., a two-liquid type, a polishing solution set for CMP), and the preparation method and usage method differ depending on the type. (a) The standard type is a polishing solution that can be used as is without pretreatment such as dilution during polishing. (b) The concentrated type is a polishing solution in which the contained components are concentrated compared to the standard type (a) in consideration of convenience for storage or transportation. (c) The multi-liquid type is a polishing solution in which the contained components are kept in a state divided into multiple liquids (e.g., a first liquid containing a certain component and a second liquid containing a different component) during storage or transportation, and these liquids are mixed and used when in use.

[0100] (a) A standard type can be obtained by dissolving or dispersing abrasive particles and additives in water, which is the main dispersion medium. For example, to prepare 1000g of polishing liquid containing 0.5 parts by mass of abrasive particles and 0.1 parts by mass of additives per 100 parts by mass of polishing liquid, the amount of abrasive particles and additives can be adjusted so that the total amount of polishing liquid contains 5g of abrasive particles and 1g of additives.

[0101] The preparation of the polishing solution can be carried out, for example, using a stirrer, a homogenizer, an ultrasonic disperser, a wet ball mill, etc. Additionally, in order to ensure that the average particle size of the abrasive particles is within a desired range, a process of micronizing the abrasive particles may be performed during the preparation of the polishing solution. The micronization of the abrasive particles can be carried out by a sedimentation classification method or by a method using a high-pressure homogenizer. The sedimentation classification method is a method comprising a process of forcibly settling a slurry containing abrasive particles using a centrifuge and a process of extracting only the supernatant. On the other hand, the method using a high-pressure homogenizer is a method of causing abrasive particles in a dispersion medium to collide with each other at high pressure.

[0102] (b) The concentrated type is diluted with water immediately before use to achieve the desired content of the contained ingredients. After dilution, stirring may be performed for any duration until liquid phase characteristics (pH, particle size of abrasives, etc.) and polishing characteristics (polishing rate of silicon oxide, polishing selectivity ratio of silicon oxide and silicon nitride, etc.) equivalent to those of the (a) conventional type are obtained. In this (b) concentrated type, since the volume decreases with increasing concentration, storage and transportation costs can be reduced.

[0103] The concentration ratio may be 1.5 times or more, 2 times or more, 3 times or more, or 5 times or more. If the concentration ratio is 1.5 times or more, it tends to be easier to obtain advantages regarding storage and transportation compared to cases where it is less than 1.5 times. The concentration ratio may be 40 times or less, 20 times or less, or 15 times or less. If the concentration ratio is 40 times or less, it tends to be easier to suppress the aggregation of particles compared to cases where it exceeds 40 times.

[0104] (c) The multi-liquid type has the advantage of avoiding aggregation of abrasive particles compared to the (b) concentrated type by appropriately dividing each liquid (first liquid, second liquid, etc.). Here, the components contained in each liquid are optional. (c) The multi-liquid type (CMP polishing liquid set) is a polishing liquid set for obtaining a polishing liquid by mixing a first liquid (slurry) and a second liquid (additive liquid). (c) In the multi-liquid type, the components of the CMP polishing liquid are divided into the first liquid and the second liquid, the first liquid contains abrasive particles and water, and the second liquid contains at least one of the additives and water. (c) In the first embodiment of the multi-liquid type, the first liquid contains abrasive particles and water, and the second liquid contains at least one selected from the group consisting of component (A1) and component (A2), component (B), and water. (c) In the second embodiment of the multiple liquid type, the first liquid comprises a pulp, at least one selected from the group consisting of component (A1) and component (A2), and water, and the second liquid comprises component (B) and water. (c) In the third embodiment of the multiple liquid type, the first liquid comprises a pulp, one of component (A1) and component (A2), component (B), and water, and the second liquid comprises the other of component (A1) and component (A2) and water. (c) In the fourth embodiment of the multiple liquid type, the first liquid comprises a pulp, component (B), and water, and the second liquid comprises at least one selected from the group consisting of component (A1) and component (A2), and water. The first liquid and the second liquid may include other components that are mixed as needed. In this case, to increase the dispersibility of the particles in the first solution, any acid or alkali may be added to the first solution to adjust the pH.

[0105] (c) A multi-liquid type polishing solution is useful when the combination of components tends to degrade relatively quickly due to aggregation of abrasive particles when mixed. Additionally, from the perspective of reducing storage and transportation costs, at least one of the solutions (first solution, second solution, etc.) may be a concentrated type. In this case, when using the polishing solution, each solution and water may be mixed. The concentration ratio and pH of each solution are arbitrary, and the final mixture must be made to be equivalent to (a) a conventional type polishing solution in terms of liquid phase characteristics and polishing characteristics.

[0106] <Polishing Method>

[0107] The polishing method according to the present embodiment includes a polishing process for polishing a surface to be polished using a polishing liquid according to the present embodiment. The polishing liquid used in the polishing process may be a polishing liquid obtained by mixing the first liquid and the second liquid in the polishing liquid set described above. That is, the polishing method according to the present embodiment may include a polishing process for polishing a surface to be polished using a polishing liquid obtained by mixing the first liquid and the second liquid in the polishing liquid set described above.

[0108] The polishing method according to the present embodiment uses a polishing solution in which the content of each component, pH, etc., are adjusted, and can flatten a substrate having a silicon oxide film on its surface using CMP technology. The polishing method according to the present embodiment is suitable for polishing that requires high speed, high flatness, and low polishing damage, such as polishing ILD films, and is suitable for applications where a large number of ILD films are polished in a short time.

[0109] The polishing process may be a process in which the polishing liquid according to the present embodiment is supplied between a gas and a polishing member (a polishing member, a polishing pad, etc.) and the gas is polished by the polishing member. The polishing method according to the present embodiment is suitable for polishing a gas having a silicon oxide film on its surface. Therefore, the surface to be polished may contain silicon oxide, and the polishing process may be a process in which the polishing liquid according to the present embodiment is supplied between the silicon oxide film on the surface of the gas having a silicon oxide film and the polishing member and the silicon oxide film is polished by the polishing member.

[0110] The polishing method according to the present embodiment is suitable for polishing a substrate having a silicon oxide film on its surface during the manufacturing process of a device. Examples of devices include individual semiconductors such as diodes, transistors, compound semiconductors, thermistors, varistors, and thyristors; memory elements such as DRAM (Dynamic Random Access Memory), SRAM (Static Random Access Memory), EPROM (Erasable Programmable Read Only Memory), Mask ROM (Mask Read Only Memory), EEPROM (Electronic Erasable Programmable Read Only Memory), and flash memory; theoretical circuit elements such as microprocessors, DSPs, and ASICs; integrated circuit elements such as compound semiconductors represented by MMICs (Monolithic Microwave Integrated Circuits); hybrid integrated circuits (hybrid ICs); light-emitting diodes; and photoelectric conversion elements such as charge-coupled devices.

[0111] According to one aspect of the polishing liquid according to the present embodiment, a high polishing speed can be achieved without significantly depending on the uneven shape of the surface to be polished. Therefore, the polishing method using said polishing liquid can be applied even to gases for which it was difficult to achieve a high polishing speed using conventional polishing liquids.

[0112] The polishing method according to the present embodiment is suitable for flattening a surface to be polished that has a step (irregularity) on its surface. Examples of a substrate having such a surface to be polished include, for instance, a logic semiconductor device. Furthermore, the polishing method according to the present embodiment is suitable for polishing a surface that includes a portion in which the concave or convex portions are in a T-shape or a grid shape when viewed from above. For example, the polishing method according to the present embodiment can also polish a silicon oxide film provided on the surface of a semiconductor device (such as a DRAM or flash memory) having a memory cell at a high speed. These indicate that it was difficult to achieve a high polishing speed using conventional polishing solutions for CMP, and that one aspect of the polishing solution according to the present embodiment can achieve a high polishing speed without significantly depending on the irregular shape of the surface to be polished.

[0113] The gas is not limited to a gas having only a silicon oxide film on its surface, but may also be a gas having a silicon nitride film, a polycrystalline silicon film, etc., on its surface in addition to a silicon oxide film. The gas may also be a gas having an inorganic insulating film such as silicon oxide, glass, or silicon nitride; or a film mainly containing polysilicon, Al, Cu, Ti, TiN, W, Ta, TaN, etc., on a wiring board having a predetermined wiring.

[0114] Hereinafter, as an example of a process including a polishing method according to the present embodiment, a process for forming an ILD film (interlayer insulating film) structure by CMP will be described. FIG. 1 is a schematic cross-sectional view showing the process of polishing an ILD film and the process of forming an ILD film between wirings. FIG. 1 (a) is a schematic cross-sectional view showing the state before polishing. FIG. 1 (b) is a schematic cross-sectional view showing the state after polishing.

[0115] As shown in FIG. 1(a), in the substrate (100) before polishing, wiring (20) is formed on a lower substrate (not shown) having a predetermined lower wiring (not shown) with an ILD film (10) interposed therebetween, and a silicon oxide film (30) is formed to cover the wiring (20). Since the silicon oxide film (30) is formed on the ILD film (10) on which the wiring (20) is formed, the portion on the wiring (20) is higher than the other portion, and thus a step (D) is created on the surface of the silicon oxide film (30). The wiring (20) is connected to the lower wiring, etc. by a contact plug (40) formed to penetrate the ILD film (10).

[0116] In the process of forming the ILD film structure, in order to eliminate the step difference (D), unnecessary parts that are partially protruding on the surface of the silicon oxide film (30) are first removed by CMP. To polish the silicon oxide film (30), a gas (100) is placed on a polishing member so that the surface of the silicon oxide film (30) and the polishing member come into contact, and the surface of the silicon oxide film (30) is polished by this polishing member. More specifically, the silicon oxide film (30) is polished by pressing the side of the surface to be polished (surface) of the silicon oxide film (30) against the polishing member of a polishing plate, and by supplying a polishing liquid between the surface to be polished and the polishing member while moving the two relatively. Thus, the step difference (D) is eliminated, and finally, as shown in (b) of FIG. 1, the height of the wiring (20) portion on the surface of the silicon oxide film (30) and the height of the other portion become almost the same, and a gas (100a) having a silicon oxide film (30) (ILD film) with a flat surface is obtained.

[0117] As a polishing device used for polishing, for example, a device equipped with a holder for maintaining gas, a polishing plate to which a polishing pad is attached, and a means for supplying polishing liquid onto the polishing pad may be used. Examples of polishing devices include polishing devices manufactured by Ebara Seisakusho Co., Ltd. (model numbers: EPO-111, EPO-222, F-REX200, and F-REX300) and polishing devices manufactured by Applied Materials (product names: Mirra3400 and Reflexion). There are no particular restrictions on the constituent material of the polishing pad, and for example, general nonwoven fabric, expanded polyurethane, porous fluoropolymer, etc., may be used. In addition, the polishing pad may be formed with grooves to allow the polishing liquid to be retained.

[0118] As for the grinding conditions, there are no specific restrictions, but in order to prevent gas from being emitted, the rotation speed of the grinding plate is 200 min -1 The following may be acceptable. The pressure (processing load) applied to the gas may be 100 kPa or less, from the perspective of facilitating the suppression of abrasive scratches on the surface to be polished. During polishing, the polishing liquid may be continuously supplied to the polishing pad by means of a pump, etc. There is no limit to this supply amount, but the surface of the polishing pad may always be covered with the polishing liquid. After polishing is finished, the gas may be thoroughly washed in flowing water, and then the water droplets attached to the gas may be removed using a spin dryer, etc., and then dried.

[0119] By polishing as described above, surface irregularities can be eliminated, and a smooth surface can be obtained over the entire surface of the body. In addition, by repeating the process of forming a film and polishing the film a predetermined number of times, a structure having a desired number of layers can be manufactured.

[0120] The substrate (structure) obtained in this manner can be used as various electronic components. Specific examples of electronic components include semiconductor devices; optical glass such as photomasks, lenses, and prisms; inorganic conductive films such as ITO; optical integrated circuits, optical switching devices, and optical waveguides composed of glass and crystalline materials; optical single crystals such as cross-sections of optical fibers and scintillators; solid-state laser single crystals; sapphire substrates for blue laser LEDs; semiconductor single crystals such as SiC, GaP, and GaAs; glass substrates for magnetic disks; magnetic heads, etc.

[0121] <Manufacturing method, etc.>

[0122] The method for manufacturing a part according to the present embodiment comprises a part manufacturing process in which a part is obtained using a body (a workpiece to be polished) polished by the polishing method according to the present embodiment. The part according to the present embodiment is a part obtained by the method for manufacturing a part according to the present embodiment. The part according to the present embodiment is not particularly limited, but may be an electronic part (e.g., a semiconductor part such as a semiconductor package), a wafer (e.g., a semiconductor wafer), or a chip (e.g., a semiconductor chip). As one aspect of the method for manufacturing a part according to the present embodiment, in the method for manufacturing an electronic part according to the present embodiment, an electronic part is obtained using a body polished by the polishing method according to the present embodiment. As one aspect of the method for manufacturing a part according to the present embodiment, in the method for manufacturing a semiconductor part according to the present embodiment, a semiconductor part (e.g., a semiconductor package) is obtained using a body polished by the polishing method according to the present embodiment. The method for manufacturing a part according to the present embodiment may comprise a polishing process in which a body is polished by the polishing method according to the present embodiment prior to the part manufacturing process.

[0123] The method for manufacturing a component according to the present embodiment may include, as one aspect of the component manufacturing process, a fragmentation process for fragmenting a body (a workpiece to be polished) polished by the polishing method according to the present embodiment. The fragmentation process may, for example, be a process of obtaining a chip (for example, a semiconductor chip) by dicing a wafer (for example, a semiconductor wafer) polished by the polishing method according to the present embodiment. As one aspect of the method for manufacturing a component according to the present embodiment, the method for manufacturing an electronic component according to the present embodiment may include a process for obtaining an electronic component (for example, a semiconductor component) by fragmenting a body polished by the polishing method according to the present embodiment. As one aspect of the method for manufacturing a component according to the present embodiment, the method for manufacturing a semiconductor component according to the present embodiment may include a process for obtaining a semiconductor component (for example, a semiconductor package) by fragmenting a body polished by the polishing method according to the present embodiment.

[0124] The method for manufacturing a part according to the present embodiment may include, as one aspect of the part manufacturing process, a connection process in which a body (a member to be polished) polished by the polishing method according to the present embodiment is connected to another body (e.g., electrically connected). The body connected to the body polished by the polishing method according to the present embodiment is not particularly limited; it may be the body polished by the polishing method according to the present embodiment, or it may be a body different from the body polished by the polishing method according to the present embodiment. In the connection process, the body and the body may be connected directly (connected in a state where the body and the body are in contact), or the body and the body may be connected through another member (such as a conductive member). The connection process may be performed before the remodeling process, after the remodeling process, or before and after the remodeling process.

[0125] The connection process may be a process of connecting a surface to be polished of a body polished by the polishing method according to the present embodiment to a body to be connected, or a process of connecting a connection surface of a body polished by the polishing method according to the present embodiment to a connection surface of a body to be connected. The connection surface of the body may be a surface to be polished polished by the polishing method according to the present embodiment. By the connection process, a connection body comprising a body and a body to be connected can be obtained. In the connection process, if the connection surface of the body has a metal part, the body to be connected may be brought into contact with the metal part. In the connection process, if the connection surface of the body has a metal part and the connection surface of the body to be connected also has a metal part, the metal parts may be brought into contact with each other. The metal part may include copper.

[0126] The device according to the present embodiment (e.g., an electronic device such as a semiconductor device) comprises at least one type selected from the group consisting of a body polished by the polishing method according to the present embodiment and a part according to the present embodiment.

[0127] Examples

[0128] The present disclosure will be explained in more detail below by way of examples, but the present disclosure is not limited to these examples.

[0129] <Production of Cerium Oxide Powder>

[0130] 40 kg of hydrated cerium carbonate was divided into 10 alumina containers and calcined in air at 830°C for 2 hours to obtain a total of 20 kg of yellowish-white powder. Phase identification was performed on this powder using X-ray diffraction, confirming that the powder contains polycrystalline cerium oxide. SEM observation of the particle size of the powder obtained by calcination revealed a range of 20 to 100 μm. Subsequently, cerium oxide powder A (the powder imparting the abrasive grain A described later) was obtained by dry grinding the 20 kg of cerium oxide powder using a jet mill. The specific surface area of ​​cerium oxide powder A after grinding was 9.4 m² 2 It was / g. The specific surface area was measured by the BET method.

[0131] Preparation of Slurry

[0132] 15.0 kg of the cerium oxide powder obtained above and 84.5 kg of deionized water were placed in a container and mixed. Next, 0.5 kg of 1 M (mol / L, about 6 mass%) acetic acid was added, and the mixture was stirred for 10 minutes to obtain a cerium oxide mixture. This cerium oxide mixture was transferred to another container for 30 minutes. During this time, the cerium oxide mixture was subjected to ultrasonic irradiation at an ultrasonic frequency of 400 kHz within the transfer pipe.

[0133] A cerium oxide mixture, which had been processed through ultrasonic irradiation, was placed in four 1000 mL polyethylene containers at a rate of 800 g ± 8 g each. The cerium oxide mixture in each container was centrifuged for 20 minutes under conditions where the centrifugal force applied to the outer circumference was 500 G. After centrifugation, the supernatant fraction of the container was collected to obtain a slurry. The slurry contained approximately 10.0 mass% of cerium oxide particles (grains B) based on the total mass.

[0134] A sample for particle size measurement was obtained by diluting the slurry with pure water so that the abrasive particle content was 0.25 mass% based on the total mass. For this sample, the average particle size of the abrasive particles was measured using a laser diffraction and scattering particle size distribution measuring device (Microtrac BEL Corp., product name: Microtrac MT3300EXII), and the average particle size was 140 nm.

[0135] <CMP용 연마액의 제작>

[0136] By mixing the above-described slurry, each additive, and deionized water in the following order, polishing solutions having the composition of each of the following tables (remainder: deionized water) were obtained. In the tables, "THEED" refers to 2,2',2',2'''-ethylenedinitrilotetrateethanol, and "EDTP" refers to 1,1',1'',1'''-ethylenedinitrilotetrate-2-propanol. Each polishing solution contains acetic acid mixed during the preparation of the above-described slurry, in an amount corresponding to the respective abrasive particle content.

[0137] Specifically, an additive solution was obtained by dissolving each additive in deionized water. Next, the above-described slurry and the additive solution were mixed in equal amounts and stirred for 10 minutes to obtain a concentrated stock solution for polishing containing 5.0 mass% of abrasive particles based on total mass. The stock solution for polishing contains 20 times the amount of abrasive particles and additives relative to the abrasive particle content of 0.25 mass% of the final polishing solution, and 5 times the amount of abrasive particles and additives relative to the abrasive particle content of 1.00 mass% of the final polishing solution.

[0138] Then, by diluting the stock solution for the polishing solution with deionized water 20 times, the polishing solutions of Examples A1, A4 and Comparative Example A1 were obtained. In addition, by diluting the stock solution for the polishing solution with deionized water 5 times, the polishing solutions of Examples A2 to A3, B1 to B6 and Comparative Examples A2 to A3 and B1 were obtained. For the polishing solutions of each example, when the abrasive content was 0.25 mass% based on total mass (for polishing solutions with an abrasive content of 1.00 mass%, when the abrasive content was adjusted to 0.25 mass%), the average particle size of the abrasives was equivalent to the average particle size of the abrasives in the slurry described above.

[0139] Zeta Potential Measurement

[0140] An appropriate amount of polishing liquid was added to "DelsaNano C," a product manufactured by Beckmann Coulter Inc., and measurements were taken twice at 25°C. The average value of the indicated zeta potentials was obtained as the zeta potential. In each of the examples and comparative examples, the zeta potential of the abrasive particles was positive.

[0141] <pH 측정>

[0142] (pH of the polishing solution)

[0143] The pH of the polishing solution was measured under the following conditions. The results are shown in each table.

[0144] Measured temperature: 25℃

[0145] Measuring device: Product name of Horiba Seisakusho Co., Ltd.: Model (D-71)

[0146] Measurement method: After calibrating the pH meter at three points using phthalate pH standard solution (pH: 4.01), neutral phosphate pH standard solution (pH: 6.86), and borate pH standard solution (pH: 9.18) as pH standard solutions, the electrode of the pH meter was placed in the polishing solution, and the pH after stabilization was measured by the above measuring device after 2 minutes or more.

[0147] <Evaluation of Grinding Characteristics>

[0148] (Preparation of evaluation wafer)

[0149] As a blanket wafer (BKW), a φ200mm unpatterned wafer having a silicon oxide film (SiO2, initial film thickness: 1000nm) on its surface was prepared.

[0150] As a pattern wafer (PTW), a wafer (company-made, φ200 mm) with a test pattern attached to a silicon oxide film (initial film thickness: 7200 nm) having an uneven surface pattern was prepared. The convex portion (Line portion) has an initial step height 6000 nm higher than the concave portion (Space portion), and the convex portion is intended for polishing evaluation of high step height and low density protrusions by etch-back. The pattern wafer has multiple 26 mm × 26 mm die units, and within each die unit, there are multiple (4) 13 mm × 13 mm unit areas, and as one of the unit areas, an evaluation was performed in a parallel line pattern area where the Line / Space (L / S) is 30 μm / 570 μm (density of the convex portion: 5%).

[0151] (Grinding Procedure)

[0152] The evaluation wafer described above was polished using a polishing device (manufactured by Applied Materials, product name: Mirra3400). The evaluation wafer described above was set in a holder having an adsorption pad for gas attachment. A polishing pad made of porous urethanum resin (K-groove, manufactured by DuPont (Dow), model number: IC-1010) was attached to a polishing plate with a diameter of 500 mm.

[0153] The aforementioned holder was placed on the polishing pad with the polishing surface of the aforementioned evaluation wafer facing downward. The inner tube pressure, retainer ring pressure, and membrane pressure were set to 14 kPa, 21 kPa, and 14 kPa, respectively.

[0154] Then, while dropping the aforementioned polishing liquid onto the polishing pad attached to the aforementioned polishing plate at a flow rate of 200 mL / min, the polishing plate and the evaluation wafer are each 93 min -1 and 87 min-1 The surface to be polished was polished by rotating it. For the blanket wafer, polishing was performed for 30 seconds. For the pattern wafer, polishing was performed for 60 seconds, which is the polishing time during which a convex portion remains after polishing. Subsequently, the evaluation wafer after polishing was thoroughly washed with pure water using a PVA brush (polyvinyl alcohol brush) and then dried.

[0155] (Evaluation of grinding speed)

[0156] The change in film thickness of the film to be polished before and after polishing was measured using an optical interference film thickness measuring device (manufactured by Nanometrics Japan Co., Ltd., Product Name: AFT-5100) as follows, and the polishing rate was obtained. The results are shown in each table.

[0157] For the blanket wafer, the change in film thickness was measured at a total of 41 measurement points (20 points on each side of the center point) at the center point of the wafer and at intervals of 5 mm in the radial direction from the center point (the measurement point following the one at 95 mm from the center was set at 97 mm from the center). The change in film thickness was measured at these 41 points during a polishing time of 30 seconds, and the average value was obtained as the polishing speed of the blanket wafer.

[0158] In the pattern wafer, the change in film thickness at one location in the convex part (30 μm width line) of the central part of the pattern of L / S = 30 μm / 570 μm in the central die unit (26 mm × 26 mm) of the pattern wafer was measured to obtain the polishing speed of the pattern wafer.

[0159] [Table 1]

[0160]

[0161] [Table 2]

[0162] Explanation of the symbols

[0163] 10… ILD membrane 20… wiring 30… silicon oxide film 40… contact plug 100, 100a… gas D… Step

Claims

Claim 1 A polishing solution for CMP comprising abrasive particles, an additive, and water, wherein the abrasive particles comprise cerium-based particles, and the additive comprises (A1) a 4-pyrone-based compound represented by the following general formula (1) and (B) a compound having two or more nitrogen atoms bonded to a hydroxyalkyl group, and wherein the component (B) comprises a compound represented by the following general formula (I). [Chemical Formula 1] [During the meal, X 11 , X 12 and X 13 Each is independently a hydrogen atom or a monovalent substituent. [In the expression, n is an integer greater than or equal to 1, and R 11 , R 12 , R 13 and R 14 Each independently represents a hydrogen atom or an organic group, and R 11 and R 12 One or both are hydroxyalkyl groups, and R 13 and R 14 One or both are hydroxyalkyl groups. Claim 2 A polishing solution for CMP according to claim 1, wherein the (A1) component comprises at least one selected from the group consisting of 3-hydroxy-2-methyl-4-pyrone, 5-hydroxy-2-(hydroxymethyl)-4-pyrone, and 2-ethyl-3-hydroxy-4-pyrone. Claim 3 A polishing solution for CMP according to claim 1, wherein the content of the (A1) component is 0.001 to 5 mass%. Claim 4 A polishing solution for CMP according to claim 1, wherein the component (B) comprises ethylenedinitrilotetarethanol. Claim 5 A polishing solution for CMP according to claim 1, wherein the component (B) comprises ethylenedinitrilotetarpapanol. Claim 6 A polishing solution for CMP according to claim 1, wherein the content of component (B) is 0.001 to 5 mass%. Claim 7 A polishing solution for CMP according to claim 1, wherein the additive further comprises a saturated monocarboxylic acid. Claim 8 A polishing solution for CMP according to claim 1, having a pH of 8.0 or less. Claim 9 A polishing solution for CMP comprising abrasive particles, an additive, and water, wherein the abrasive particles comprise cerium-based particles, and the additive comprises (A2) picolinic acid and (B) a compound having two or more nitrogen atoms bonded to a hydroxyalkyl group, and wherein the component (B) comprises a compound represented by the following general formula (I). [In the expression, n is an integer greater than or equal to 1, and R 11 , R 12 , R 13 and R 14 Each independently represents a hydrogen atom or an organic group, and R 11 and R 12 One or both are hydroxyalkyl groups, and R 13 and R 14 One or both are hydroxyalkyl groups. Claim 10 A polishing liquid for CMP according to claim 9, wherein the content of the (A2) component is 0.001 to 5 mass%. Claim 11 A polishing solution for CMP according to claim 9, wherein the component (B) comprises ethylenedinitrilotetarethanol. Claim 12 A polishing solution for CMP according to claim 9, wherein the (B) component comprises ethylenedinitrilotetarpapanol. Claim 13 A polishing solution for CMP according to claim 9, wherein the content of component (B) is 0.001 to 5 mass%. Claim 14 A polishing solution for CMP according to claim 9, having a pH of 8.0 or less. Claim 15 A set of polishing liquids for CMP, wherein the components of the polishing liquid for CMP described in any one of claims 1 to 14 are divided and preserved into a first liquid and a second liquid, wherein the first liquid comprises the abrasive particles and water, and the second liquid comprises at least one of the additives and water. Claim 16 A polishing method comprising a process of polishing a surface to be polished using a polishing liquid for CMP described in any one of claims 1 to 14. Claim 17 A polishing method according to claim 16, wherein the surface to be polished comprises silicon oxide. Claim 18 A polishing method comprising a process of polishing a surface to be polished using a CMP polishing liquid obtained by mixing the first liquid and the second liquid in the CMP polishing liquid set described in claim 15. Claim 19 A polishing method according to claim 18, wherein the surface to be polished comprises silicon oxide.

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