Slurry, polishing method, component production method, and semiconductor component production method

Abstract

This slurry contains abrasive grains containing alumina particles, a water-soluble polymer, and water. After the alumina particles are hydrothermally treated at 200°C for 10 hours, differential thermogravimetric analysis (DTG) is performed. In a DTG curve in which the horizontal axis represents the measurement temperature T and the vertical axis represents ΔWT / (W×S) defined below, a peak is observed in a range of 400-500°C.　ΔWT: the weight reduction amount of alumina particles at the measurement temperature T; W: the mass of alumina particles used for differential thermogravimetric analysis; S: the BET specific surface area of the alumina particles

Description

Slurry, polishing method, method for manufacturing parts, and method for manufacturing semiconductor parts

[0001] This disclosure relates to slurry, polishing methods, methods for manufacturing parts, methods for manufacturing semiconductor parts, etc.

[0002] In the semiconductor field, with the increasing performance of ultra-large-scale integrated circuits (ULSIs), it is becoming increasingly difficult to achieve both high integration and high speed through miniaturization techniques that are merely extensions of conventional technologies. Therefore, technologies are being developed that allow for both miniaturization of semiconductor elements and high integration in the vertical direction (i.e., technologies for multi-layer wiring).

[0003] One such technique is hybrid bonding using resin materials. In hybrid bonding, the resin portion (the portion containing resin material) on the metal portion (the portion containing metal material: a metal pattern formed by photolithography (copper pattern, tin-silver alloy pattern, etc.)) is removed by polishing (e.g., CMP (chemical mechanical polishing)), thereby obtaining an exposed surface where the metal and resin portions are exposed. This exposed surface can then be bonded to the object to be bonded. The resin portion can be obtained, for example, by supplying a curable resin material onto the metal portion and then curing the resin material.

[0004] CMP (Computer Polishing) is typically performed using a device that can supply polishing fluid onto a polishing pad. The surface of the workpiece is polished by supplying polishing fluid between the workpiece and the polishing pad while pressing the workpiece against the polishing pad. Thus, in CMP technology, the polishing fluid is one of the key technologies, and various polishing fluids have been developed to obtain high-performance polishing fluids (see, for example, Patent Document 1 below).

[0005] Japanese Patent Publication No. 2008-288537

[0006] For slurries that can be used as polishing fluids to polish the resin parts of the workpiece, it is sometimes required to achieve a high polishing speed for the resin material.

[0007] Therefore, one aspect of this disclosure aims to provide a slurry capable of achieving a high polishing speed for resin materials. Another aspect of this disclosure aims to provide a polishing method using the slurry. Yet another aspect of this disclosure aims to provide a method for manufacturing parts using the polishing method. Yet another aspect of this disclosure aims to provide a method for manufacturing semiconductor parts using the polishing method.

[0008] This disclosure includes, for example, the following aspects: [1] A material containing abrasive grains containing alumina particles, a water-soluble polymer, and water, wherein the alumina particles are hydrothermally treated at 200°C for 10 hours, and then differential thermogravimetric analysis (DTG) is performed, with the horizontal axis being the measured temperature T and the vertical axis being ΔW as defined below. Ｔ In the DTG curve defined as (W × S), a peak is observed in the range of 400-500°C. Ｔ : Weight loss of alumina particles at measurement temperature T W: Mass of alumina particles used in differential thermogravimetric analysis S: BET specific surface area of ​​alumina particles [2] The BET specific surface area is 0.1 to 20 m² ２[1] The slurry according to [1], wherein the amount is / g. [3] The slurry according to [1] or [2], wherein the average particle size of the alumina particles is 100 to 2000 nm. [4] The slurry according to any one of [1] to [3], wherein the water-soluble polymer contains polyvinylpyrrolidone. [5] The slurry according to any one of [1] to [4], wherein the content of the water-soluble polymer is 0.1 to 5% by mass. [6] The slurry according to any one of [1] to [5], further containing an organic acid component. [7] The slurry according to [6], wherein the organic acid component contains glycine. [8] The slurry according to [6] or [7], wherein the content of the organic acid component is 0.1 to 5% by mass. [9] The slurry according to any one of [1] to [8], further containing an organic solvent.

[10] The slurry according to [9], wherein the organic solvent contains 3-methoxy-3-methyl-1-butanol.

[11] A slurry according to any one of [1] to

[10] , wherein the pH is 1.0 to 7.0.

[12] A polishing method comprising the step of polishing a workpiece using a slurry according to any one of [1] to

[11] .

[13] The polishing method according to

[12] , wherein the workpiece comprises a polyimide resin.

[14] A method for manufacturing a part, comprising the step of obtaining a part using the workpiece polished by the polishing method according to

[12] or

[13] .

[15] A method for manufacturing a semiconductor part, comprising the step of obtaining a semiconductor part using the workpiece polished by the polishing method according to

[12] or

[13] .

[0009] According to one aspect of this disclosure, a slurry capable of achieving a high polishing speed for resin materials can be provided. According to another aspect of this disclosure, a polishing method using the slurry can be provided. According to yet another aspect of this disclosure, a method for manufacturing parts using the polishing method can be provided. According to yet another aspect of this disclosure, a method for manufacturing semiconductor parts using the polishing method can be provided.

[0010] The embodiments of this disclosure will be described below.

[0011] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. "A or greater" in a numerical range means A and the range greater than A. "A or less" in a numerical range means A and the range less than A. In numerical ranges described stepwise in this specification, the upper or lower limit of a numerical range in one step can 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 that numerical range may be replaced 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 specified, the materials exemplified in this specification can be used individually or in combination of two or more. The content of each component in a composition means the total amount of multiple substances present in the composition if there are multiple substances corresponding to each component in the composition, unless otherwise specified. The term "process" includes not only independent processes, but also any process that cannot be clearly distinguished from other processes, as long as its intended function is achieved.

[0012] <Slurry> The slurry according to this embodiment may be a slurry for polishing resin materials (slurry for resin materials), and can be used to polish a surface containing a resin material, and can be used as a CMP polishing solution. Examples of resin materials include polyimide resin, epoxy resin, acrylic resin (polymer having structural units derived from monomers having (meth)acryloyl groups), polybenzoxazole resin, phenol resin, etc. The resin material may include at least one selected from the group consisting of polyimide resin, epoxy resin, acrylic resin, polybenzoxazole resin, and phenol resin. The resin material may have carbon-carbon bonds. The resin material may be a photosensitive resin or a non-photosensitive resin (a resin that does not have photosensitivity).

[0013] Polyimide resins have excellent electrical insulation properties and can be used as insulating layers between different metal layers and between wires. Examples of methods for forming a film of a polyimide resin include a method in which a thin film is formed from a polyimide solution by spin coating, dip coating, spray coating, or the like, and the polyimide resin film is formed by heating and / or light irradiation.

[0014] The slurry according to the present embodiment comprises abrasive grains containing alumina particles, a water-soluble polymer, and water. After subjecting the alumina particles to hydrothermal treatment at 200°C for 10 hours, differential thermogravimetry (DTG) is performed, with the measurement temperature T on the horizontal axis and ΔW on the vertical axis Ｔ / (W×S) in the DTG curve, a peak is observed in the range of 400 to 500°C. Note that ΔW Ｔ represents the weight loss amount of the alumina particles at the measurement temperature T, W represents the mass of the alumina particles used for differential thermogravimetry, and S represents the BET specific surface area of the alumina particles. According to the slurry according to the present embodiment, a resin material can be polished at a high polishing rate.

[0015] According to the slurry according to the present embodiment, in the evaluation described in the examples below, a polishing rate of, for example, 200 nm / min or more (preferably 500 nm / min or more, 700 nm / min or more, 900 nm / min or more, 1100 nm / min or more, 1400 nm / min or more, 1700 nm / min or more, 2000 nm / min or more, 2300 nm / min or more, etc.) can be obtained for a resin material.

[0016] According to one aspect of the slurry according to the present embodiment, the resin material can be polished at a higher polishing rate compared to the case where the slurry does not contain a water-soluble polymer. The effect that a higher polishing rate can be obtained when the slurry contains a water-soluble polymer than when the slurry does not contain a water-soluble polymer is referred to as a boost effect. The boost effect can be confirmed by calculating the ratio of the polishing rate of a slurry containing a water-soluble polymer to the polishing rate of a slurry not containing a water-soluble polymer (polishing rate of slurry containing a water-soluble polymer / polishing rate of slurry not containing a water-soluble polymer; this ratio is also referred to as boost magnification). If the boost magnification is more than 1.00, it can be said that there is a boost effect.

[0017] According to one aspect of the slurry according to the present embodiment, in the evaluation described in the Examples below, a boost ratio of more than 1.00 (preferably 1.10 or more, 1.20 or more, 1.30 or more, 1.40 or more, 1.50 or more, 1.60 or more, 1.70 or more, 1.80 or more, 1.90 or more, 2.00 or more, 2.10 or more, 2.20 or more, 2.30 or more, 2.40 or more, 2.50 or more, 2.60 or more, 2.70 or more, 2.80 or more, 2.90 or more, 3.00 or more, etc.) can be achieved.

[0018] The reason why a resin material can be polished at a high polishing rate is not clear, but the following reasons are exemplified. However, the reason why the above-described effect is obtained is not limited to the following content. That is, when the water-soluble polymer adheres to the resin material, the resin material is denatured, the molecular chains of the resin material are cut, and the mechanical strength of the resin material decreases. In addition, since the water-soluble polymer also adheres to fragments of the resin material generated by polishing, the water-soluble polymer adhering to the resin material on the surface to be polished repels the water-soluble polymer adhering to the fragments of the resin material, thereby suppressing adhesion of the fragments of the resin material to the surface to be polished. Furthermore, when alumina particles are subjected to hydrothermal treatment, water is adsorbed onto the alumina particles. When thermogravimetric differential analysis is performed after the hydrothermal treatment, let the horizontal axis be measurement temperature T and the vertical axis be ΔW Ｔ / (W×S) in the DTG curve of the alumina particles, the peak observed in the range of 400 to 500°C is considered to result from desorption of water adsorbed to the alumina particles. When this peak is observed, it can be said that the alumina particles have high hydrophilicity. Highly hydrophilic alumina particles are easily dispersed in the slurry, which increases the number of alumina particles contributing to polishing. In addition, it is presumed that the higher the hydrophilicity of the alumina particles, the higher the interaction with the resin material, so the chemical reactivity of the alumina particles is improved, and a high polishing rate for the insulating material can be obtained.

[0019] The slurry according to the present embodiment can be used, for example, for polishing in a wiring formation step of a semiconductor device or the like. The slurry according to the present embodiment can be suitably used not only for polishing a resin material used as a constituent material of a hard mask, but also for polishing an interlayer insulating film using a resin material, and the like.

[0020] (Abrasive Grains) The slurry according to the present embodiment contains abrasive grains including alumina particles. Examples of the abrasive grains include α-alumina particles and γ-alumina particles. The alumina particles may be α-alumina particles from the viewpoints of easily obtaining a high polishing rate for resin materials and easily obtaining a high boosting effect. The alumina particles may include colloidal alumina from the viewpoints of easily obtaining a high polishing rate for resin materials, easily obtaining a high boosting effect, making it difficult for defects such as scratches to occur on the polished surface of the object to be polished, and easily improving the flatness of the polished surface. The alumina particles may be surface-treated alumina particles from the viewpoints of improving the dispersibility of the alumina particles, easily obtaining a high polishing rate for resin materials, easily obtaining a high boosting effect, making it difficult for defects such as scratches to occur on the polished surface of the object to be polished, and easily improving the flatness of the polished surface.

[0021] After hydrothermally treating alumina particles at 200°C for 10 hours, differential thermogravimetry (DTG) is performed, where the horizontal axis represents the measured temperature T and the vertical axis represents ΔW Ｔ In a DTG curve with / (W×S), a peak is observed in the range of 400 to 500°C.

[0022] The hydrothermal treatment is a process in which 0.5 g of a sample is placed in a small bottle (e.g., Labor screw vial No. 2), 2 g of pure water is placed in a sealed container (e.g., HU-100 manufactured by Sanai Kagaku Co., Ltd.), then the small bottle containing the sample is placed therein, and heating is performed at 200°C for 10 hours so that the sample does not come into direct contact with liquid water. Specifically, it may be the process described in the Examples below.

[0023] Differential thermogravimetry (DTG) is performed using a simultaneous differential thermogravimetry device (e.g., STA300 manufactured by Hitachi High-Tech Corporation), with a temperature increase rate of 10°C / min, a measurement interval of 30 seconds, and a flow rate of synthetic air of 100 mL / min, to measure the mass and temperature of the alumina particles at each measurement. The temperature range for performing differential thermogravimetry is 25 to 1100°C. Through differential thermogravimetry, the horizontal axis represents the measured temperature T, and the vertical axis represents ΔW Ｔ A DTG curve with / (W×S) can be obtained. ΔW ＴThis is the weight loss of the alumina particles at the measurement temperature T, and can be calculated from the difference between the mass of the alumina particles at the measurement temperature T and the mass of the alumina particles at the time of the previous measurement (i.e., the measurement 30 seconds prior to the measurement at the measurement temperature T).

[0024] In the DTG curve of alumina particles, the maximum peak observed in the 400-500°C range is 0.0010 g / m², which is considered to be the optimal value from the viewpoint of improving the hydrophilicity of the alumina particles, making it easier to obtain high polishing speeds for resin materials, and also from the viewpoint of easily obtaining a high boost effect. ２ Above, 0.0030g / m ２ Above, 0.0050g / m ２ Above, 0.010g / m ２ Above, 0.020g / m ２ Above, 0.030g / m ２ Above, 0.040g / m ２ Above or equal to 0.045 g / m² ２ The above is acceptable. The peak maximum value is set at 0.20 g / m² from the viewpoint of easily obtaining a high polishing speed for resin materials and easily obtaining a high boost effect. ２ Below, 0.18g / m ２ Below, 0.16g / m ２ Below, 0.14g / m ２ Below, 0.12g / m ２ Below, 0.10g / m ２ Below, 0.090g / m ２ Below, 0.080g / m ２ Below, 0.070g / m ２ The following, or 0.060 g / m² ２ The following may be true. From these perspectives, the peak maximum value is 0.0010–0.20 g / m³. ２ ,0.0010~0.14g / m ２ ,0.0010~0.090g / m ２ ,0.0010~0.060g / m ２ ,0.010~0.20g / m ２ ,0.010~0.14g / m ２ ,0.010~0.090g / m ２ ,0.010~0.060g / m ２ ,0.040~0.20g / m ２,0.040~0.14g / m ２ ,0.040~0.090g / m ２ , or 0.040 to 0.060 g / m ２ That's fine.

[0025] Methods for adjusting the maximum value of the peak observed in the 400-500°C range in the DTG curve of alumina particles include changing the alumina particle manufacturing conditions, the grinding method, and other related methods. These methods may be used individually or in combination.

[0026] The BET specific surface area S of alumina particles is set to 20 m, from the perspective of achieving a high polishing speed for resin materials and a high boost effect, as the physical strength of the alumina particles is increased by reducing the pore structure of the alumina particles. ２ / g or less, 15m ２ / g or less, 12m ２ Less than 10m / g ２ / g or less, 8m ２ / g or less, 6m ２ / g or less, or 5m ２ It may be less than or equal to / g. The BET specific surface area S is set to 0.1m from the viewpoint of easily obtaining a high polishing speed for resin materials and easily obtaining a high boost effect, as a larger surface area of ​​alumina particles increases the number of reaction sites on the surface of the alumina particles, thereby improving chemical reactivity. ２ / g or more, 0.3m ２ / g or more, 0.5m ２ / g or more, or 1m ２ It may be 1 / g or more. From these viewpoints, the BET specific surface area S is 0.1 to 20 m². ２ / g, 0.3-10m ２ / g, or 0.5-5m ２ It may be / g. The BET specific surface area S can be obtained by the method described in the examples below. Note that the BET specific surface area S is measured on alumina particles that have not undergone hydrothermal treatment.

[0027] The average particle size of alumina particles may be 100 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 400 nm or more, 500 nm or more, greater than 500 nm, 550 nm or more, 600 nm or more, 650 nm or more, or 700 nm or more, as this ensures sufficient physical polishing ability per alumina particle, and thus facilitates obtaining a high polishing speed for resin materials and a high boost effect. The average particle size of alumina particles may be 750 nm or more, 800 nm or more, 850 nm or more, or 900 nm or more. The average particle size of alumina particles may be 5000 nm or less, 4500 nm or less, 4000 nm or less, 3500 nm or less, 3000 nm or less, 2500 nm or less, 2000 nm or less, less than 2000 nm, 1900 nm or less, 1800 nm or less, 1700 nm or less, 1600 nm or less, 1500 nm or less, less than 1500 nm, 1400 nm or less, 1300 nm or less, 1200 nm or less, 1100 nm or less, 1000 nm or less, or less than 1000 nm, as this makes it easier to ensure a sufficient number of alumina particles per unit area in contact with the surface to be polished, and from the viewpoint of easily obtaining a high polishing speed for resin materials and easily obtaining a high boost effect. The average particle size of alumina particles may be 900 nm or less, 800 nm or less, 700 nm or less, or 600 nm or less. From these perspectives, the average particle size of the alumina particles may be 100-5000 nm, 100-3000 nm, 100-2000 nm, 100-1500 nm, 100-1000 nm, 300-5000 nm, 300-3000 nm, 300-2000 nm, 300-1500 nm, 300-1000 nm, 500-5000 nm, 500-3000 nm, 500-2000 nm, 500-1500 nm, or 500-1000 nm. The average spherical diameter of the abrasive grains may be within the above range.

[0028] The "average particle size" is the volume-average particle size, which is the secondary particle size of the alumina particles or abrasive grains. It can be obtained by measuring the particle size of the alumina particles or abrasive grains in the slurry, or the particle size of the alumina particles or abrasive grains before they are mixed into the slurry. The average particle size can be measured using a light diffraction scattering particle size analyzer, or by preparing a sample in which alumina particles or abrasive grains are dispersed in water and measuring it. For example, using a COULTER N4SD from COULTER Electronics, measurements can be taken under the following conditions: measurement temperature: 20°C, solvent refractive index: 1.333 (water), particle refractive index: Unknown (set), solvent viscosity: 1.005 cp (water), Run Time: 200 seconds, laser incidence angle: 90°, and Intensity (scattering intensity, equivalent to turbidity): 5E+04 to 4E+05. If the intensity is higher than 4E+05, the sample can be diluted with water before measurement. Colloidal particles are usually obtained dispersed in water, so they can also be appropriately diluted to fall within the above-mentioned scattering intensity range before measurement.

[0029] The alumina particle content in the abrasive grains may be 50% by mass or more, more than 50% by mass, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 99% by mass or more, based on the total mass of the abrasive grains (the entire mass of abrasive grains contained in the slurry), from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boost effect. The abrasive grains may be composed of alumina particles (substantially 100% by mass of the abrasive grains contained in the slurry are alumina particles).

[0030] The abrasive content may be within the following ranges based on the total mass of the slurry. The abrasive content may be 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 5% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less, from the viewpoint of easily obtaining a high polishing speed for the resin material, easily obtaining a high boost effect, and easily suppressing the occurrence of scratches, as the amount of abrasive per unit area of ​​the surface to be polished is reduced, making it easier for the water-soluble polymer to preferentially contact the surface to be polished, thereby promoting the modification of the resin material. The abrasive content may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 0.9% by mass or more, or 1% by mass or more, from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boost effect, as the number of times the abrasive comes into contact with the surface to be polished per unit time is increased. From these perspectives, the abrasive content may be 0.01 to 20% by mass, 0.01 to 10% by mass, 0.01 to 5% by mass, 0.01 to 2% by mass, 0.1 to 20% by mass, 0.1 to 10% by mass, 0.1 to 5% by mass, 0.1 to 2% by mass, 0.5 to 20% by mass, 0.5 to 10% by mass, 0.5 to 5% by mass, 0.5 to 2% by mass, 0.9 to 20% by mass, 0.9 to 10% by mass, 0.9 to 5% by mass, or 0.9 to 2% by mass.

[0031] (Additives) The slurry according to this embodiment contains additives. "Additives" refers to substances contained in the slurry other than abrasive grains and water.

[0032] [Water-soluble polymer] The slurry according to this embodiment contains a water-soluble polymer. A "water-soluble polymer" is defined as a polymer that dissolves in 0.1 g or more of water per 100 g. The inclusion of a water-soluble polymer in the slurry makes it easier to obtain a high polishing speed and a high boost effect on the resin material.

[0033] Examples of water-soluble polymers include ether polymers such as polyoxyethylene, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene naphthyl ether, polyoxypropylene polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl allyl ether, and polyoxyethylene polyoxypropylene ether derivatives; glycerin polymers such as polyglycerin and polyglycerin derivatives; polycarboxylic acids such as polyacrylic acid and polymaleic acid; acrylic polymers such as polyacrylamide and polydimethylacrylamide; polysaccharides such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, agar, curdlan, dextrin, cyclodextrin, and pullulan; vinyl polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrolein, and poly-N-vinylacetamide; and oxazoline polymers such as polyoxazoline. The water-soluble polymer may contain vinyl polymers, and may contain at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, and polyacrolein, and may contain polyvinylpyrrolidone. By containing at least one selected from the group consisting of polyvinylpyrrolidone, polyoxyethylene distyleninated phenyl ether, polyoxazoline, hydroxyethylcellulose, hydroxypropylcellulose, polyethylene oxide, and poly-N-vinylacetamide, it becomes easier to obtain a high polishing speed and a high boost effect on the resin material.

[0034] Water-soluble polymers may contain surfactants. In this specification, a surfactant means a substance that has both hydrophilic and hydrophobic groups in its molecule, and includes ionic surfactants and nonionic surfactants. Examples of hydrophilic groups include hydroxyl groups, carboxyl groups, sulfone groups, amino groups, ether groups, and ester groups. Examples of hydrophobic groups include alkyl groups, phenyl groups, naphthyl groups, and alkenyl groups.

[0035] Examples of surfactants include ether-type surfactants such as polyglycerin, polyglycerin fatty acid esters, polyglycerin lauryl acid esters, polyglycerin derivatives, polyoxyethylene distyleninated phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene naphthyl ether, polyoxypropylene polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene ether derivatives, polyoxypropylene glyceryl ether, polyethylene glycol, methoxypolyethylene glycol, acetylene glycol, and polyoxyethylene polyoxypropylene glycol; amino ether-type surfactants such as polyoxyethylene alkylamines; ether ester-type surfactants such as polyoxyethylene glycerol borate fatty acid esters and polyoxyethylene alkyl esters; and alkanolamide-type surfactants such as polyoxyethylene fatty acid alkanolamides.

[0036] When the resin material is a resin material containing nitrogen atoms (for example, polyimide resin), the water-soluble polymer may also contain a water-soluble polymer containing nitrogen atoms (nitrogen-containing water-soluble polymer) from the viewpoint of easily obtaining a high polishing speed of the resin material and easily obtaining a high boost effect. By including a nitrogen-containing water-soluble polymer in the water-soluble polymer, the affinity between the water-soluble polymer (nitrogen-containing water-soluble polymer) and the resin material containing nitrogen atoms is increased, making it easier to obtain a high polishing speed and a high boost effect of the resin material.

[0037] Examples of nitrogen-containing water-soluble polymers include polyacrylamide, polydimethylacrylamide, polyvinylpyrrolidone, poly-N-vinylacetamide, polyoxazoline, polyoxyethylene alkylamine, and polyoxyethylene fatty acid alkanolamide.

[0038] The water-soluble polymer may have a cyclic structure, from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boost effect. When the water-soluble polymer has a cyclic structure, it becomes bulkier. When such a water-soluble polymer adheres to the fragments of resin material generated by polishing, the water-soluble polymer adhering to the resin material on the polished surface and the water-soluble polymer adhering to the fragments of resin material become more repelled, further suppressing the adhesion of the fragments of resin material to the polished surface, and making it easier to obtain a high polishing speed and a high boost effect for the resin material.

[0039] The weight-average molecular weight of the water-soluble polymer may be within the following ranges, from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boost effect: The weight-average molecular weight of the water-soluble polymer may be 1000 or more, 3000 or more, 5000 or more, 6000 or more, 7000 or more, 8000 or more, or 9000 or more. The weight-average molecular weight of the water-soluble polymer may be 100000 or less, 50000 or less, 30000 or less, 20000 or less, 15000 or less, 12000 or less, or 11000 or less. From these perspectives, the weight-average molecular weight of water-soluble polymers may be 1,000 to 100,000, 1,000 to 30,000, 1,000 to 15,000, 1,000 to 11,000, 5,000 to 100,000, 5,000 to 30,000, 5,000 to 15,000, 5,000 to 11,000, 7,000 to 100,000, 7,000 to 30,000, 7,000 to 15,000, 7,000 to 11,000, 9,000 to 100,000, 9,000 to 30,000, 9,000 to 15,000, or 9,000 to 11,000. The weight-average molecular weight of vinyl polymers and polyvinylpyrrolidone may be within the above ranges.

[0040] The weight-average molecular weight can be measured, for example, using gel permeation chromatography (GPC) under the following conditions. Sample: 20 μL Standard polyethylene glycol: Polymer Laboratory Co., Ltd., standard polyethylene glycol (molecular weight: 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, and 23000) Detector: Resona Corporation, RI-Monitor, product name "Shodex-RI SE-61" Pump: Hitachi, Ltd., product name "L-6000" Column: Resona Corporation product names "GS-220HQ" and "GS-620HQ" linked in this order Eluent: 0.4 mol / L sodium chloride aqueous solution Measurement temperature: 30°C Flow rate: 1.00 mL / min Measurement time: 45 min

[0041] The content of water-soluble polymers may be within the following ranges based on the total mass of the slurry, from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boost effect: The content of water-soluble polymers may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, or 0.5% by mass or more. The content of water-soluble polymers may be 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.7% by mass or less, 0.6% by mass or less, or 0.5% by mass or less. From these viewpoints, the content of water-soluble polymers may be 0.01 to 5% by mass, 0.01 to 1% by mass, 0.01 to 0.7% by mass, 0.1 to 5% by mass, 0.1 to 1% by mass, 0.1 to 0.7% by mass, 0.3 to 5% by mass, 0.3 to 1% by mass, or 0.3 to 0.7% by mass. The content of vinyl polymers and polyvinylpyrrolidone may be within the above ranges.

[0042] The mass ratio of the water-soluble polymer content to the abrasive content (water-soluble polymer content / abrasive content) may be within the following ranges from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boost effect. The mass ratio may be 0.01 or more, 0.05 or more, 0.1 or more, 0.3 or more, 0.4 or more, or 0.5 or more. The mass ratio may be 20 or less, 10 or less, 5 or less, 1 or less, 0.7 or less, or 0.5 or less. From these viewpoints, the mass ratio may be 0.01 to 20, 0.01 to 5, 0.01 to 1, 0.01 to 0.7, 0.1 to 20, 0.1 to 5, 0.1 to 1, 0.1 to 0.7, 0.4 to 20, 0.4 to 5, 0.4 to 1, or 0.4 to 0.7. The mass ratio of the vinyl polymer content to the abrasive content (vinyl polymer content / abrasive content), and the mass ratio of the polyvinylpyrrolidone content to the abrasive content (polyvinylpyrrolidone content / abrasive content) may be within the ranges described above.

[0043] [Organic Acid Components] The slurry according to this embodiment may contain organic acid components. Examples of organic acid components include organic acids and their salts (for example, alkali metal salts such as sodium salts; alkaline earth metal salts such as calcium salts). By using organic acid components, the resin material is modified, making it easier to obtain a high polishing speed and a high boost effect for the resin material.

[0044] Examples of organic acids include saturated fatty acids such as formic acid, acetic acid, and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and adipic acid; hydroxy acids such as malic acid and citric acid; and amino acids, which will be discussed later.

[0045] The slurry may contain at least one amino acid component selected from the group consisting of amino acids and amino acid derivatives, from the viewpoint of easily obtaining a high polishing speed for resin materials and easily obtaining a high boost effect. Amino acids are compounds that have both an amino group and a carboxyl group as functional groups. Examples of amino acid derivatives include amino acid esters, amino acid salts, peptides, etc. The amino acid component can be used as a pH adjuster to adjust the pH of the slurry.

[0046] The amino acid components include glycine, α-alanine, β-alanine (also known as 3-aminopropanoic acid), 2-aminobutyric acid, norvaline, valine, leucine, norleucine, isoleucine, alloisoleucine, phenylalanine, proline, sarcosine, ornithine, lysine, serine, threonine, allothreonine, homoserine, tyrosine, 3,5-diiodotyrosine, β-(3,4-dihydroxyphenyl)-alanine, thyroxine, 4-hydroxyproline, cysteine, methionine, ethionine, lanthionine, cystathionine, cystine, and cysteine. Examples include acids, aspartic acid, glutamic acid, S-(carboxymethyl)-cysteine, 4-aminobutyric acid, asparagine, glutamine, azacerin, arginine, canavanine, citrulline, δ-hydroxylysine, creatine, kynurenine, histidine, 1-methylhistidine, 3-methylhistidine, ergothioneine, tryptophan, glycylglycine, glycylglycylglycine, vasopressin, oxytocin, cassinin, eledoisin, glucagon, secretin, proopiomelanocortin, enkephalin, prodinorphine, etc. The amino acid component may include glycine from the viewpoint of easily obtaining a high polishing speed for resin materials and easily obtaining a high boost effect.

[0047] The glycine content in the organic acid component or amino acid may be 50% by mass or more, more than 50% by mass, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 99% by mass or more, based on the total mass of the organic acid component or amino acid (total amino acids contained in the slurry), from the viewpoint of easily obtaining a high polishing speed of the resin material and easily obtaining a high boost effect. The organic acid component or amino acid may consist of glycine (substantially 100% by mass of the organic acid component or amino acid contained in the slurry is glycine).

[0048] The content of organic acid components may be within the following ranges based on the total mass of the slurry, from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boost effect. The content of organic acid components may be 0.001% by mass or more, 0.005% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, or 0.5% by mass or more. The content of organic acid components may be 10% by mass or less, 5% by mass or less, 3% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.7% by mass or less, 0.6% by mass or less, or 0.5% by mass or less. From these viewpoints, the content of organic acid components may be 0.001 to 10% by mass, 0.005 to 5% by mass, 0.01 to 3% by mass, 0.1 to 1% by mass, or 0.3 to 0.8% by mass. The content of amino acid components and glycine may be within the above-mentioned range.

[0049] The mass ratio of the organic acid component content to the abrasive grain content (organic acid component content / abrasive grain content) may be within the following ranges from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boost effect. The mass ratio may be 0.01 or more, 0.05 or more, 0.1 or more, 0.3 or more, 0.4 or more, or 0.5 or more. The mass ratio may be 20 or less, 10 or less, 5 or less, 1 or less, 0.7 or less, or 0.5 or less. From these viewpoints, the mass ratio may be 0.01 to 20, 0.01 to 5, 0.01 to 1, 0.01 to 0.7, 0.1 to 20, 0.1 to 5, 0.1 to 1, 0.1 to 0.7, 0.4 to 20, 0.4 to 5, 0.4 to 1, or 0.4 to 0.7. The mass ratio of the amino acid component content to the abrasive grain content (amino acid component content / abrasive grain content), and the mass ratio of the glycine content to the abrasive grain content (glycine content / abrasive grain content) may be within the ranges described above.

[0050] The mass ratio of the content of organic acid components to the content of water-soluble polymers (content of organic acid components / content of water-soluble polymers) may be within the following ranges from the viewpoint of easily obtaining a high polishing speed of the resin material and easily obtaining a high boost effect. The mass ratio may be 0.01 or more, 0.05 or more, 0.1 or more, 0.5 or more, or 1 or more. The mass ratio may be 20 or less, 10 or less, 5 or less, 2 or less, or 1 or less. From these viewpoints, the mass ratio may be 0.01 to 20, 0.05 to 10, 0.1 to 5, or 0.5 to 2. The mass ratio of the content of amino acid components to the content of water-soluble polymers (content of amino acids / content of water-soluble polymers), and the mass ratio of the content of glycine to the content of abrasive grains (content of glycine / content of water-soluble polymers) may be within the above ranges.

[0051] [Organic solvent] The slurry according to this embodiment may contain an organic solvent (excluding compounds corresponding to organic acid components). The inclusion of an organic solvent in the slurry makes it easier to obtain a high polishing speed and a high boost effect on the resin material.

[0052] As the organic solvent, any solvent that can be mixed with water can be used. Examples of organic solvents include: carbonate esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactone compounds such as butyrolactone and propiolactone; glycol compounds such as ethylene glycol, propylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; and derivatives of glycol compounds such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monoethyl ether. Glycol monoethers (e.g., glycol monoalkyl ethers) such as diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, diethylene glycol monopropyl ether, dipropylene glycol monopropyl ether, triethylene glycol monopropyl ether, tripropylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether, and tripropylene glycol monobutyl ether;Glycol diethers such as ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, diethylene glycol dipropyl ether, dipropylene glycol dipropyl ether, triethylene glycol dipropyl ether, tripropylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether, triethylene glycol dibutyl ether, tripropylene glycol dibutyl ether, etc.; tetrahydrofuran, geo Ether compounds such as xane, dimethoxyethane, polyethylene oxide, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate; alcohols such as methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, and isopropanol; 2-methoxyethanol, 2-ethoxyethanol, 2-(2-methoxy)ethoxyethanol, 2-(2-butoxyethoxy)ethanol, 2-propoxyethanol, and 2-butoxyethanol. Toxyethanol, 3-methoxy-3-methyl-1-butanol, 2-(methoxymethoxy)ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2-isopentyloxyethanol, 1-propoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 1-methoxy-2-butanol, glycol monoethers and other alkoxy alcohols; acetone, methyl ethyl ketone and other ketones; phenol; dimethylformamide; N-methylpyrrolidone;Examples include ethyl acetate, ethyl lactate, and sulfolane.

[0053] The organic solvent may contain an alkoxy alcohol, and may also contain 3-methoxy-3-methyl-1-butanol, from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boosting effect.

[0054] The content of the organic solvent may be within the following ranges based on the total mass of the slurry. The content of the organic solvent may be 0.001% by mass or more, 0.005% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, 0.08% by mass or more, 0.09% by mass or more, or 0.1% by mass or more, from the viewpoint of easily obtaining sufficient wettability of the slurry to the substrate, easily obtaining a high polishing speed of the resin material, and easily obtaining a high boost effect. The content of the organic solvent may be 10% by mass or less, 5% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.5% by mass or less, 0.3% by mass or less, or 0.1% by mass or less, from the viewpoint of easily obtaining a high polishing speed of the resin material, easily obtaining a high boost effect, and easily reducing the possibility of ignition. From these perspectives, the content of the organic solvent may be 0.001 to 10% by mass, 0.01 to 3% by mass, 0.05 to 1% by mass, or 0.08 to 0.5% by mass. The content of 3-methoxy-3-methyl-1-butanol may be within the above range.

[0055] The mass ratio of the organic solvent content to the abrasive content (organic solvent content / abrasive content) may be within the following ranges from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boost effect. The mass ratio may be 0.001 or more, 0.01 or more, 0.03 or more, 0.05 or more, 0.08 or more, or 0.1 or more. The mass ratio may be 5 or less, 2 or less, 1 or less, 0.5 or less, 0.3 or less, or 0.1 or less. From these viewpoints, the mass ratio may be 0.001 to 5, 0.001 to 1, 0.001 to 0.3, 0.03 to 5, 0.03 to 1, 0.03 to 0.3, 0.08 to 5, 0.08 to 1, or 0.08 to 0.3. The mass ratio of the 3-methoxy-3-methyl-1-butanol content to the abrasive grain content (3-methoxy-3-methyl-1-butanol content / abrasive grain content) may be within the range described above.

[0056] The mass ratio of the organic solvent content to the water-soluble polymer content (organic solvent content / water-soluble polymer content) may be within the following ranges from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boost effect. The mass ratio may be 0.001 or more, 0.01 or more, 0.03 or more, 0.05 or more, 0.1 or more, or 0.2 or more. The mass ratio may be 5 or less, 2 or less, 1 or less, 0.5 or less, 0.3 or less, or 0.2 or less. From these viewpoints, the mass ratio may be 0.001 to 5, 0.001 to 1, 0.001 to 0.3, 0.03 to 5, 0.03 to 1, 0.03 to 0.3, 0.1 to 5, 0.1 to 1, or 0.1 to 0.3. The mass ratio of the content of 3-methoxy-3-methyl-1-butanol to the content of water-soluble polymers (content of 3-methoxy-3-methyl-1-butanol / content of water-soluble polymers) may be within the range described above.

[0057] The mass ratio of the organic solvent content to the organic acid content (organic solvent content / organic acid content) may be within the following ranges from the viewpoint of easily obtaining a high polishing speed for the resin material and easily obtaining a high boost effect. The mass ratio may be 0.001 or more, 0.01 or more, 0.03 or more, 0.05 or more, 0.1 or more, or 0.2 or more. The mass ratio may be 5 or less, 2 or less, 1 or less, 0.5 or less, 0.3 or less, or 0.2 or less. From these viewpoints, the mass ratio may be 0.001 to 5, 0.001 to 1, 0.001 to 0.3, 0.03 to 5, 0.03 to 1, 0.03 to 0.3, 0.1 to 5, 0.1 to 1, or 0.1 to 0.3. The mass ratio of the content of 3-methoxy-3-methyl-1-butanol to the content of organic acid components (content of 3-methoxy-3-methyl-1-butanol / content of organic acid components) may be within the range described above.

[0058] [Other Additives] The slurry according to this embodiment may contain additives other than the components described above. Examples of such additives include pH adjusters and polymer materials.

[0059] The slurry according to this embodiment may contain a basic component as a pH adjusting agent. Examples of basic components include sodium hydroxide, ammonia (e.g., aqueous ammonia), potassium hydroxide, calcium hydroxide, and the like.

[0060] The base component content may be within the following ranges based on the total mass of the slurry: The base component content may be greater than 0% by mass, 0.00001% by mass or more, 0.00005% by mass or more, 0.0001% by mass or more, 0.0005% by mass or more, 0.001% by mass or more, or 0.005% by mass or more. The base component content may be 10% by mass or less, 5% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less, 0.05% by mass or less, 0.01% by mass or less, 0.005% by mass or less, or 0.001% by mass or less. The content of the base component is more than 0% by mass and not more than 10% by mass, more than 0% by mass and not more than 1% by mass, more than 0% by mass and not more than 0.1% by mass, more than 0% by mass and not more than 0.01% by mass, more than 0% by mass and not more than 0.001% by mass, 0.00005-10% by mass, 0.00 005-1% by weight, 0.00005-0.1% by weight, 0.001-10% by weight, 0.001-1% by weight, 0.001-0.1% by weight, 0.001-0.01% by weight, or 0.001-0.001% by weight.

[0061] (Water) The slurry according to this embodiment contains water. The water content in the slurry may be the remainder obtained by subtracting the content of other components from the total amount of slurry. The water content may be 50% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, based on the total mass of the slurry. The slurry according to this embodiment may be stored as a slurry storage liquid with a lower water content than that used during polishing. In this case, the slurry can be obtained by diluting the storage liquid with water during polishing.

[0062] (pH) The pH of the slurry according to this embodiment may be 7.0 or less, less than 7.0, 6.5 or less, 6.0 or less, less than 6.0, 5.5 or less, 5.3 or less, 5.2 or less, 5.1 or less, 5.0 or less, less than 5.0, 4.9 or less, 4.8 or less, 4.7 or less, or 4.6 or less, from the viewpoint of easily obtaining a high polishing speed of the resin material and easily obtaining a high boost effect. The pH of the slurry may be 1.0 or more, 1.2 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, greater than 3.0, 3.5 or more, 4.0 or more, greater than 4.0, 4.1 or more, 4.2 or more, 4.3 or more, 4.4 or more, 4.5 or more, greater than 4.5, or 4.6 or more, from the viewpoint of easily obtaining a high polishing speed of the resin material and easily obtaining a high boost effect. From these perspectives, the pH of the slurry may be 1.0–7.0, 1.0–6.0, 1.0–5.0, 1.0–4.6, 2.0–7.0, 2.0–6.0, 2.0–5.0, 2.0–4.6, 3.0–7.0, 3.0–6.0, 3.0–5.0, 3.0–4.6, 4.0–7.0, 4.0–6.0, 4.0–5.0, or 4.0–4.6. The pH of the slurry is defined as the pH at a liquid temperature of 25°C.

[0063] The pH of the slurry according to this embodiment can be measured using a pH meter (for example, a Model (F-51) manufactured by Horiba, Ltd.). For example, the pH meter is calibrated 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 calibration solutions. After that, the electrode of the pH meter is placed in the slurry, and the value is measured after it has stabilized for at least two minutes. At this time, the temperature of the calibration solution and the slurry should be 25°C.

[0064] <Polishing Method> The polishing method according to this embodiment comprises a polishing step of polishing a resin material using a slurry according to this embodiment. In the polishing step, the surface to be polished, including the resin material, may be polished using the slurry according to this embodiment, or the surface to be polished of a material to be polished, including the resin material, may be polished. In the polishing step, the surface to be polished of a hard mask, including the resin material, may be polished using the slurry according to this embodiment. In the polishing step, the surface to be polished, including the metal material, may be polished using the slurry according to this embodiment, or the surface to be polished of a material to be polished, including the metal material, may be polished. The slurry used in the polishing step may be a slurry obtained by diluting a storage liquid with water. The surface to be polished may have a layer containing at least one selected from the group consisting of resin material and metal material.

[0065] In the polishing process, for example, the surface to be polished of the substrate is pressed against the polishing cloth of the polishing platen, and while a predetermined pressure is applied to the substrate from the side opposite to the surface to be polished (the back side of the substrate), the slurry according to this embodiment is supplied between the surface to be polished of the substrate and the polishing cloth, and the surface to be polished can be polished by moving the substrate relative to the polishing platen.

[0066] As a polishing apparatus, for example, when polishing with an abrasive cloth, a general polishing apparatus can be used that has a holder capable of holding the substrate to be polished, and a polishing platen to which an abrasive cloth can be attached, which is connected to a motor with a changeable rotation speed. As the abrasive cloth, general nonwoven fabrics, foamed polyurethane, porous fluororesin, etc. can be used.

[0067] There are no restrictions on the polishing conditions, but the rotation speed of the polishing platen should be 200 rpm (rpm = min) to prevent the base material from flying off. －１ The rotation speed may be as low as ) or less. The pressure applied to the polishing cloth by the substrate (such as a semiconductor substrate) having the surface to be polished may be 1 to 100 kPa or 5 to 50 kPa, from the viewpoint of easily satisfying uniformity of polishing speed within the polished surface and flatness of the pattern. During polishing, slurry can be continuously supplied to the polishing cloth by a pump or the like. There is no limit to the amount supplied, but the surface of the polishing cloth may always be covered with slurry.

[0068] To ensure that the surface condition of the polishing cloth remains constant during polishing (CMP, etc.), a conditioning step for the polishing cloth may be performed before polishing. For example, the polishing cloth can be conditioned using a dresser with diamond particles and a liquid containing at least water. Subsequently, after performing the polishing method according to this embodiment, a substrate cleaning step may be further performed. After polishing, the substrate may be thoroughly washed in running water, and then dried after removing any water droplets adhering to the substrate using a spin dryer or the like. Alternatively, a known cleaning method (for example, a method in which a commercially available cleaning solution is poured onto the substrate surface while a polyurethane brush is rotated and pressed against the substrate with constant pressure to remove any adhering material) may be performed before drying.

[0069] The slurry and polishing method according to this embodiment may be applied not only to film-like objects to be polished, but also to various substrates made of glass, silicon, SiC, SiGe, Ge, GaN, GaP, GaAs, sapphire, plastic, etc.

[0070] The slurry and polishing method according to this embodiment can be used not only for the manufacture of semiconductor devices, but also for the manufacture of image display devices such as TFT liquid crystals and organic ELs; optical components such as photomasks, lenses, prisms, optical fibers, and single-crystal scintillators; optical elements such as optical switching elements and optical waveguides; light-emitting elements such as solid-state lasers and blue laser LEDs; and magnetic storage devices such as magnetic disks and magnetic heads.

[0071] <Manufacturing Method, etc.> The manufacturing method of the component according to this embodiment includes a component manufacturing step of obtaining a component using a substrate (a member to be polished) polished by the polishing method according to this embodiment. The component according to this embodiment is a component obtained by the manufacturing method of the component according to this embodiment. The component according to this embodiment is not particularly limited, but may be an electronic component (for example, a semiconductor component such as a semiconductor package), a wafer (for example, a semiconductor wafer), or a chip (for example, a semiconductor chip). As one embodiment of the manufacturing method of the component according to this embodiment, in the manufacturing method of an electronic component according to this embodiment, an electronic component is obtained using a substrate polished by the polishing method according to this embodiment. As one embodiment of the manufacturing method of the component according to this embodiment, in the manufacturing method of a semiconductor component according to this embodiment, a semiconductor component (for example, a semiconductor package) is obtained using a substrate polished by the polishing method according to this embodiment. The manufacturing method of the component according to this embodiment may include a polishing step of polishing the substrate by the polishing method according to this embodiment before the component manufacturing step.

[0072] The method for manufacturing a component according to this embodiment may include, as one aspect of the component manufacturing process, a piece-forming step of dividing the substrate (a member to be polished) polished by the polishing method according to this embodiment into individual pieces. The piece-forming step may be, for example, a step of dicing a wafer (e.g., a semiconductor wafer) polished by the polishing method according to this embodiment to obtain a chip (e.g., a semiconductor chip). As one aspect of the method for manufacturing a component according to this embodiment, the method for manufacturing an electronic component according to this embodiment may include a step of obtaining an electronic component (e.g., a semiconductor component) by dividing the substrate polished by the polishing method according to this embodiment into individual pieces. As one aspect of the method for manufacturing a component according to this embodiment, the method for manufacturing a semiconductor component according to this embodiment may include a step of obtaining a semiconductor component (e.g., a semiconductor package) by dividing the substrate polished by the polishing method according to this embodiment into individual pieces.

[0073] The method for manufacturing a part according to this embodiment may include, as one aspect of the part manufacturing process, a connection step of connecting (for example, electrically connecting) a substrate (a member to be polished) polished by the polishing method according to this embodiment to another connected body. The connected body connected to the substrate polished by the polishing method according to this embodiment is not particularly limited and may be the substrate polished by the polishing method according to this embodiment, or it may be a connected body different from the substrate polished by the polishing method according to this embodiment. In the connection step, the substrate and the connected body may be directly connected (connected in a state where the substrate and the connected body are in contact), or they may be connected via another member (such as a conductive member). The connection step can be performed before the individualization step, after the individualization step, or before and after the individualization step.

[0074] The connection step may be a step of connecting the polished surface of the base body, which has been polished by the polishing method according to this embodiment, with the connected body, or it may be a step of connecting the connecting surface of the base body, which has been polished by the polishing method according to this embodiment, with the connecting surface of the connected body. The connecting surface of the base body may be the polished surface, which has been polished by the polishing method according to this embodiment. A connected body comprising a base body and a connected body can be obtained by the connection step. In the connection step, if the connecting surface of the base body has a metal part, the connected body may be brought into contact with the metal part. In the connection step, if both the connecting surface of the base body and the connecting surface of the connected body have metal parts, the metal parts may be brought into contact with each other. The metal part may contain copper.

[0075] The device according to this embodiment (for example, an electronic device such as a semiconductor device) comprises a substrate polished by the polishing method according to this embodiment, and at least one selected from the group consisting of components according to this embodiment.

[0076] The present disclosure will be further described below with reference to examples, but the present disclosure is not limited to these examples without departing from the technical concept of the present disclosure.

[0077] <Preparation of Slurry> (Examples 1-4, Comparative Examples 1-3) Abrasive particles (commercially available alumina particles; average particle size is as shown in Table 1) were mixed with deionized water. Then, polyvinylpyrrolidone (weight-average molecular weight: 10,000) was added as a water-soluble polymer, glycine as an organic acid component, and MMB (3-methoxy-3-methyl-1-butanol) as an organic solvent to obtain a slurry. Based on the total mass of the slurry, the abrasive particle content (content of alumina particles, which are the solid component) was 1% by mass, the polyvinylpyrrolidone content was 0.5% by mass (content of water-soluble polymer: 0.5% by mass), the glycine content was 0.5% by mass, and the MMB content was 0.1% by mass.

[0078] <Measurement of Average Particle Size> The average particle size (volume average particle size) of the abrasive grains (alumina particles) in the slurry was measured using a COULTER N4SD manufactured by COULTER Electronics. The results showed no change in the average particle size of the abrasive grains before and after slurry preparation. Note that "-" in the table means that measurement was not taken.

[0079] <Measurement of BET specific surface area> Each of the slurries described above was centrifuged at a centrifugal acceleration of 4700G for 30 minutes to settle the abrasive grains, and then the supernatant was removed. Next, abrasive powder was obtained by vacuum drying at room temperature (25°C) for 24 hours, and then the abrasive powder was vacuum dried at 100°C for 1 hour. Next, 0.3 to 0.4 g of the abrasive powder was weighed, and the BET specific surface area was measured using a BET specific surface area analyzer (Quantachrome Instruments, product name: QuadraSorb EVO) with liquid nitrogen (77K) as the adsorption medium by gas adsorption method at a temperature of 77K until the relative pressure reached 0.99, and an adsorption isotherm was obtained when nitrogen was used as the adsorption medium. From the obtained adsorption isotherm, the BET specific surface area S (unit: m) of the abrasive grains was measured by multipoint BET method in the relative pressure range of 0.049 to 0.30. ２ The result was obtained ( / g). The results are shown in Table 1.

[0080] <Differential Thermogravimetric Analysis (DTG)> Each of the slurries described above was centrifuged at a centrifugal acceleration of 4700G for 30 minutes to settle the abrasive particles, and then the supernatant was removed. Next, abrasive powder was obtained by vacuum drying at room temperature (25°C) for 24 hours, and then the abrasive powder was vacuum dried at 100°C for 1 hour. Next, 0.5 g of the abrasive powder was weighed into a glass screw-cap bottle, the screw-cap bottle was placed in a sealed container (San-ai Kagaku Co., Ltd., HU-100), 2 g of pure water was placed on the outside of the screw-cap bottle, and the sealed container was sealed. Next, hydrothermal treatment was performed by holding it in an oven at 200°C for 10 hours. After hydrothermal treatment, the abrasive powder was dried at 150°C.

[0081] Using a differential thermogravimetric analyzer (STA300, Hitachi High-Tech Corporation), approximately 40 mg of abrasive powder, after being hydrothermally treated and dried in a platinum pan, was weighed and measured without the use of a reference substance. The measurement was performed with a heating rate of 10°C / min, a measurement interval of 30 seconds, and a synthetic air flow rate of 100 mL / min (22% oxygen, 78% nitrogen). The mass and temperature of the abrasive powder were measured at each measurement. The horizontal axis represents the measurement temperature (T), and the vertical axis represents ΔW. Ｔ A DTG curve was obtained, denoted as ΔW / (W × S). Ｔ ΔW is the weight loss of the alumina particles at the measurement temperature T (mass of the alumina particles at the measurement temperature T - mass of the alumina particles at the measurement 30 seconds prior to the measurement at the measurement temperature T), W is the mass of the alumina particles used in differential thermogravimetric analysis, and S is the BET specific surface area of ​​the alumina particles. The presence or absence of a peak in the range of 400-500°C is checked in the obtained DTG curve, and if a peak is observed, the maximum value of the peak is ΔW. Ｔ The ratio (W × S) was measured. The results are shown in Table 1.

[0082] <pH Measurement> The pH of the slurry described above was measured using a pH meter manufactured by Horiba, Ltd., specifically the product name "Model (F-51)". Specifically, the pH meter was calibrated 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 calibration solutions. After that, the pH meter electrode was placed in the slurry, and the value was measured after it had stabilized for more than two minutes. The temperature of the calibration solutions and slurry was 25°C. The results are shown in Table 1.

[0083] <Measurement of Polishing Speed> A 12-inch diameter substrate was prepared as an evaluation test wafer, having a 10 μm thick polyimide resin layer (HD7000 series, manufactured by HD Microsystems) on a silicon substrate. The polyimide resin layer was polished (CMP) using the slurry described above under the polishing conditions below. The difference in thickness of the polyimide resin layer before and after polishing was measured using an optical film thickness gauge (Filmetrics, F54-UV), and the polishing speed of the polyimide resin was calculated based on the difference in thickness of the polyimide resin layer and the polishing time. The results are shown in Table 1.

[0084] [Polishing Conditions] Polishing equipment: Applied Materials, product name "Reflexion LK" Polishing pad: IK4250H (DuPont) Polishing pressure: 27.6 kPa (4 psi) Plate rotation speed: 87 rpm Head rotation speed: 93 rpm Slurry supply rate: 300 mL / min Polishing time: 1 minute

[0085] <Evaluation of Boost Effect> An evaluation slurry was prepared by replacing the entire amount of water-soluble polymer in the slurry described above with water. Using the evaluation slurry, polyimide resin was polished under the polishing conditions described above, and the difference in the thickness of the polyimide resin layer before and after polishing was measured. The polishing rate of the polyimide resin was calculated based on the difference in the thickness of the polyimide resin layer and the polishing time. The ratio of the polishing rate of the slurry containing water-soluble polymer to the polishing rate of the evaluation slurry (polishing rate of the slurry containing water-soluble polymer / polishing rate of the evaluation slurry) was calculated as the boost ratio. The results are shown in Table 1.

[0086]

Claims

1. The abrasive contains alumina particles, a water-soluble polymer, and water. The alumina particles are hydrothermally treated at 200°C for 10 hours, and then differential thermogravimetric analysis (DTG) is performed, with the horizontal axis representing the measured temperature T and the vertical axis representing ΔW as defined below. Ｔ In the DTG curve defined as (W × S), a peak is observed in the range of 400-500°C. Ｔ : Weight loss of alumina particles at measurement temperature T W: Mass of alumina particles used in differential thermogravimetric analysis S: BET specific surface area of ​​alumina particles 2. The BET specific surface area is 0.1 to 20 m². ２ The slurry according to claim 1, wherein the amount is / g.

3. The slurry according to claim 1, wherein the average particle size of the alumina particles is 100 to 2000 nm.

4. The slurry according to claim 1, wherein the water-soluble polymer contains polyvinylpyrrolidone.

5. The slurry according to claim 1, wherein the content of the water-soluble polymer is 0.1 to 5% by mass.

6. The slurry according to claim 1, further containing an organic acid component.

7. The slurry according to claim 6, wherein the organic acid component contains glycine.

8. The slurry according to claim 6, wherein the content of the organic acid component is 0.1 to 5% by mass.

9. The slurry according to claim 1, further comprising an organic solvent.

10. The slurry according to claim 9, wherein the organic solvent comprises 3-methoxy-3-methyl-1-butanol.

11. The slurry according to claim 1, wherein the pH is 1.0 to 7.

0.

12. A polishing method comprising the step of polishing a member to be polished using a slurry described in any one of claims 1 to 11.

13. The polishing method according to claim 12, wherein the member to be polished includes a polyimide resin.

14. A method for manufacturing a part, comprising the step of obtaining a part using the member to be polished by the polishing method described in claim 12.

15. A method for manufacturing a semiconductor component, comprising the step of obtaining a semiconductor component using the member to be polished by the polishing method described in claim 12.

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