Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09G—POLISHING COMPOSITIONS; SKI WAXES
  • C09G1/00—Polishing compositions
  • C09G1/02—Polishing compositions containing abrasives or grinding agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B24—GRINDING; POLISHING
  • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
  • B24B37/00—Lapping machines or devices; Accessories
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/14—Anti-slip materials; Abrasives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/14—Anti-slip materials; Abrasives
  • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
  • H10P95/06—Planarisation of inorganic insulating materials
  • H10P95/062—Planarisation of inorganic insulating materials involving a dielectric removal step

Definitions

• the present disclosure relates to a polishing liquid, a polishing liquid set, a polishing method, and the like.
• CMP Chemical Mechanical Polishing
• STI shallow trench isolation
• pre-metal insulating material or interlayer It has become an essential technology for flattening insulating materials, forming plugs or buried metal wiring, etc.
• a CMP polishing liquid a CMP polishing liquid containing abrasive grains containing cerium oxide is known (for example, see Patent Documents 1 and 2 below).
• One aspect of the present disclosure aims to provide a polishing liquid and a polishing liquid set that can reduce the polishing rate of silicon oxide. Another aspect of the present disclosure aims to provide a polishing method using such a polishing liquid or a polishing liquid set.
• the present disclosure relates to the following [1] to [10] and the like.
• R 1 represents an alkyl group having 1 to 10 carbon atoms
• R 2 represents an alkylene group having 1 to 10 carbon atoms
• R 3 represents a hydrogen atom or a monovalent metal atom. represent.
• the constituent components of the polishing liquid according to any one of [1] to [7] are stored separately as a first liquid and a second liquid, and the first liquid contains the abrasive grains and the polishing liquid.
• a polishing method comprising the step of polishing a polished surface containing silicon oxide using the polishing liquid according to any one of [1] to [7].
• a polishing liquid and a polishing liquid set that can reduce the polishing rate of silicon oxide. Further, according to another aspect of the present disclosure, a polishing method using such a polishing liquid can be provided.
• a numerical range indicated using “-” indicates a range that includes the numerical values written before and after "-" as the minimum and maximum values, respectively.
• the numerical range “A or more” means A and a range exceeding A.
• the numerical range “A or less” means a range of A and less than A.
• the upper limit or lower limit of the numerical range of one step can be arbitrarily combined with the upper limit or lower limit of the numerical range of another step.
• the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples.
• “A or B” may include either A or B, or may include both.
• the materials exemplified herein can be used alone or in combination of two or more, unless otherwise specified.
• the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
• process is included in the term not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved.
• the polishing liquid according to the present embodiment contains abrasive grains, an ether compound having at least one selected from the group consisting of a carboxy group and a carboxylic acid base, and water.
• the polishing liquid according to this embodiment can be used, for example, as a CMP polishing liquid.
• the polishing rate of silicon oxide it is possible to reduce the polishing rate of silicon oxide, and for example, the polishing rate of silicon oxide can be set to 400 nm/min or less.
• the polishing rate of silicon oxide may be 300 nm/min or less, 200 nm/min or less, 100 nm/min or less, 80 nm/min or less, 50 nm/min or less, or 40 nm/min or less.
• the polishing rate of silicon nitride it is possible to reduce the polishing rate of silicon nitride, and for example, the polishing rate of silicon nitride can be set to 70 nm/min or less.
• the polishing rate of silicon nitride may be 50 nm/min or less, 30 nm/min or less, 20 nm/min or less, 10 nm/min or less, or 5 nm/min or less.
• silicon oxide can be selectively polished with respect to silicon nitride.
• the polishing rate ratio of silicon oxide to silicon nitride may be 8 or more, 10 or more, 12 or more, 15 or more, 30 or more, 50 or more, or 100 or more.
• the polishing rate ratio of silicon oxide to silicon nitride may be 200 or less, 150 or less, 100 or less, 75 or less, 50 or less, or 30 or less.
• the polishing liquid according to this embodiment contains abrasive grains.
• abrasive grain refers to a collection of a plurality of particles, but for convenience, one particle constituting the abrasive grain may be referred to as an abrasive grain.
• the abrasive grains may include one or more types of particles.
• the constituent materials of the abrasive grains include inorganic materials such as cerium oxide (ceria), cerium hydroxide, silica, alumina, zirconia, titania, germania, and silicon carbide; polystyrene, polyacrylic acid, polyvinyl chloride, etc. Examples include organic matter.
• the abrasive grains may contain a cerium compound, may contain at least one selected from the group consisting of cerium oxide and cerium hydroxide, and may contain cerium oxide.
• the content of the cerium compound in the abrasive grains is determined by the polishing rate of silicon oxide. From the viewpoint of stability, more than 95% by mass, 98% by mass or more, 99% by mass or more based on the entire abrasive grain (the entire abrasive grain included in the polishing liquid or the entire particle constituting the abrasive grain) , 99.5% by mass or more, or 99.9% by mass or more.
• the abrasive grains may be substantially made of a cerium compound (an embodiment in which substantially 100% by mass of the abrasive grains is a cerium compound). From the same viewpoint, the content of cerium oxide in the abrasive grains may be in the same numerical range as the content of cerium compounds in the above-mentioned abrasive grains.
• the abrasive grains may be colloidal and may include colloidal ceria, for example.
• a polishing liquid containing colloidal abrasive grains is a suspension of abrasive grains, and has a state in which cerium oxide forming the abrasive grains is dispersed in water.
• Colloidal abrasive grains can be obtained, for example, by a liquid phase method, and are abrasive grains derived from a liquid phase method. Examples of liquid phase methods include colloid method, hydrothermal synthesis method, sol-gel method, neutralization decomposition method, hydrolysis method, chemical precipitation method, coprecipitation method, atomizing method, reverse micelle method, emulsion method, etc. .
• the abrasive grains may have grain boundaries or may not have grain boundaries.
• positron lifetime is the time it takes for a positron emitted from 22 Na to annihilate with an electron, and is used as a probe for ultrafine voids such as subnanometer to nanometer order lattice defects and free volumes. can. In other words, the shorter the positron lifetime, the higher the density of the particles.
• PAS Type L-II manufactured by Toyo Seiko Co., Ltd. can be used to measure the positron lifetime.
• the powder obtained by vacuum drying the abrasive grains at room temperature (25° C.) for 24 hours is placed in a powder measurement box, then set in the positron beam source and measured until the cumulative count reaches 1 million.
• the life histogram is separated into two components and analyzed using IPALM, which is software attached to the device. Some of the positrons emitted from 22 Na are annihilated by the positron source itself, such as Kapton or adhesive, and this component is mixed in the measurement results, so the analysis is performed assuming that the ratio of Kapton is 30%.
• ⁇ 1 and ⁇ 2 correspond to the positron lifetimes derived from the sample
• ⁇ 3 corresponds to the positron lifetimes derived from Kapton
• ⁇ 4 corresponds to the positron lifetimes derived from the adhesive.
• ⁇ 1 corresponds to a small void such as a single void
• ⁇ 2 corresponds to a void such as a cluster of a plurality of voids.
• abrasive grains on which regular diffraction spots are observed in electron beam diffraction using a transmission electron microscope (TEM) can be used.
• TEM transmission electron microscope
• the distance R between the diffraction spots is 1. 6 to 2.2 ⁇
• the minimum value of the angle ⁇ formed by diffraction spots A1 and A2 with diffraction spot B as the center is 58 to 62 degrees.
• the abrasive grains may account for 50% or more. .
• JEM-2100F manufactured by JEOL Ltd. can be used to observe the abrasive grains and measure the distance R and angle ⁇ between diffraction spots. Electron beam diffraction is performed on each abrasive grain using a TEM grit with abrasive grains attached under the conditions of acceleration voltage 200 kV, electron beam wavelength 2.508 pm, and camera length 30 cm, and distance R and angle ⁇ are measured. Can be done. The distance R and the angle ⁇ can be measured at at least three points for each abrasive grain, and the average value thereof can be used.
• the measurement is performed on all abrasive grains for which 100 or more abrasive grains are confirmed in one field of view under an arbitrary magnification in TEM observation, and the proportion of abrasive grains that satisfy the above-mentioned conditions can be calculated.
• the average particle size of the abrasive grains may be in the following range.
• the average particle size of the abrasive grains can be adjusted by natural sedimentation, pulverization, dispersion, filtration, etc.
• the particle size may be adjusted before or after mixing the components of the polishing liquid.
• the average particle diameter D50 of the abrasive grains is 1 nm or more, 3 nm or more, 5 nm or more, 10 nm or more, 30 nm or more, 50 nm or more, 80 nm or more, 100 nm or more, more than 100 nm, or 120 nm or more, from the viewpoint of easily stabilizing the polishing rate of silicon oxide. , 130 nm or more, or 140 nm or more.
• the average particle diameter D50 of the abrasive grains may be 500 nm or less, 300 nm or less, 200 nm or less, 180 nm or less, 160 nm or less, 155 nm or less, 150 nm or less, or 145 nm or less, from the viewpoint of easily stabilizing the polishing rate of silicon oxide. . From these viewpoints, the average particle diameter D50 of the abrasive grains may be 1 to 500 nm.
• the average particle diameter D50 of the abrasive grains means the 50% particle diameter of the volume-based cumulative distribution, and can be measured, for example, by a laser diffraction particle size distribution meter.
• the content of abrasive grains may be in the following range based on the total mass of the polishing liquid, from the viewpoint of easily stabilizing the polishing rate of silicon oxide.
• the content of abrasive grains is 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.08% by mass or more, 0.10% by mass or more, 0.20% by mass or more, or , 0.25% by mass or more.
• the content of abrasive grains is 10% by mass or less, 5.0% by mass or less, 3.0% by mass or less, 1.0% by mass or less, less than 1.0% by mass, 0.80% by mass or less, 0.50 It may be less than 0.50% by weight, less than 0.40% by weight, less than 0.30% by weight, or less than 0.25% by weight. From these viewpoints, the content of abrasive grains may be 0.01 to 10% by mass.
• the polishing liquid according to the present embodiment contains an ether compound (hereinafter referred to as ether compound A) having at least one type selected from the group consisting of a carboxy group and a carboxylic acid base from the viewpoint of reducing the polishing rate of silicon oxide.
• Ether compound A is a compound having one or more ether groups and one or more carboxy groups or carboxylic acid groups.
• carboxylic acid bases include functional groups in which the hydrogen atom of a carboxy group is substituted with a metal atom (sodium atom, potassium atom, etc.).
• the polishing rate of silicon oxide can be reduced. Although the reason is not clear, the polishing of silicon oxide is suppressed by the oxygen atoms of the ether group of ether compound A and the oxygen atoms of the carboxy group or carboxylic acid base attaching bidentately to the surface of the abrasive grain. It is surmised that this is because the However, this is not limited to the above reasons. Furthermore, by containing the ether compound A in the polishing liquid, the polishing rate of silicon nitride can be reduced. The reason for this is presumed to be the same as the above reason for reducing the polishing rate of silicon oxide, but is not limited to the above reason.
• the number of carbon atoms in the ether compound A may be 3 or more from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the number of carbon atoms in the ether compound A is 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, 8 or less, 6 or less, 5 or less, or 4 or less, from the viewpoint of easily reducing the polishing rate of silicon oxide. It's fine. From these viewpoints, the number of carbon atoms in the ether compound A may be 3 to 50, 3 to 30, 3 to 10, or 3 to 6.
• the number of carbon atoms in the ether compound A may be 4 or more.
• the number of carbon atoms in the ether compound A may be 3 or less.
• the molecular weight of the ether compound A may be in the following range from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the molecular weight of the ether compound A may be 50 or more, 55 or more, 60 or more, 65 or more, 70 or more, 75 or more, 80 or more, 85 or more, or 90 or more.
• the molecular weight of the ether compound A may be 500 or less, 400 or less, 300 or less, 250 or less, 200 or less, 150 or less, 130 or less, 120 or less, 115 or less, 110 or less, or 105 or less. From these viewpoints, the molecular weight of the ether compound A may be from 50 to 500.
• the molecular weight of the ether compound A may be 95 or more, or 100 or more.
• the molecular weight of ether compound A may be 100 or less, or 95 or less.
• the number of ether groups in the ether compound A may be in the following range from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the number of ether groups may be 10 or less, 8 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1.
• the number of ether groups may be one or more. From these points of view, the number of ether groups may be from 1 to 10.
• the total number of carboxy groups and carboxylic acid groups in ether compound A may be in the following range from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the total number of carboxy groups and carboxylic acid groups may be 10 or less, 8 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1.
• the total number of carboxy groups and carboxylic acid groups may be 1 or more. From these points of view, the total number of carboxy groups and carboxylic acid groups may be from 1 to 10.
• the ether compound A may have a functional group other than an ether group, a carboxy group, and a carboxylic acid group, and from the viewpoint of easily reducing the polishing rate of silicon oxide, the ether compound A may have a functional group other than an ether group, a carboxy group, and a carboxylic acid group. It is not necessary to have Examples of functional groups other than ether groups, carboxy groups, and carboxylic acid groups include hydroxy groups, epoxy groups, phosphono groups, phosphonate groups, amino groups, cyano groups, sulfo groups, and sulfonate groups.
• the total number of functional groups other than ether groups, carboxy groups, and carboxylic acid groups in ether compound A is 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, from the viewpoint of easily reducing the polishing rate of silicon oxide. It may be 2 or less, or 1 or less.
• the ether compound A may have at least one member selected from the group consisting of an aromatic ring and a heteroaromatic ring, and from the viewpoint of easily reducing the polishing rate of silicon oxide, the ether compound A may have an aromatic ring and a heteroaromatic ring. You don't have to.
• the total number of aromatic rings and heteroaromatic rings in ether compound A may be 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less, from the viewpoint of easily reducing the polishing rate of silicon oxide. .
• the ether compound A may have an unsaturated carbon-carbon bond, and does not need to have an unsaturated carbon-carbon bond from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the number of unsaturated carbon-carbon bonds in the ether compound A may be 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less, from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the ether compound A may include a chain ether compound (an ether compound without a cyclic structure) from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the ether compound A may include a compound represented by the following general formula (1) from the viewpoint of easily reducing the polishing rate of silicon oxide.
• R 1 represents an alkyl group having 1 to 10 carbon atoms
• R 2 represents an alkylene group having 1 to 10 carbon atoms
• R 3 represents a hydrogen atom or a monovalent metal atom. represent.
• the number of carbon atoms in the alkyl group of R 1 may be 8 or less, 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less, from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the number of carbon atoms in the alkyl group of R 1 may be 1 to 5 from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the number of carbon atoms in the alkyl group of R 1 may be 2 or more.
• R 1 may be an alkyl group without a substituent.
• the number of carbon atoms in the alkylene group of R 2 may be 8 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1 from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the number of carbon atoms in the alkylene group of R 2 may be 1 to 5 from the viewpoint of easily reducing the polishing rate of silicon oxide.
• R 2 may be an alkylene group without a substituent.
• the ether compound A examples include methoxyacetic acid, ethoxyacetic acid, propoxyacetic acid, butoxyacetic acid, 3-methoxypropionic acid, 2-methoxybutanoic acid, and salts thereof.
• the ether compound A may include an ether compound having a -O-CH 2 -COOR (R represents a hydrogen atom or a monovalent metal atom) structure from the viewpoint of easily reducing the polishing rate of silicon oxide, It may contain at least one selected from the group consisting of methoxyacetic acid, ethoxyacetic acid, and salts thereof.
• Ether compound A does not need to contain 2-furancarboxylic acid, 2,5-furandicarboxylic acid, diglycolic acid, and salts thereof.
• the content of ether compound A may be in the following range based on the total mass of the polishing liquid.
• the content of the ether compound A is 0.0010% by mass or more, 0.0030% by mass or more, 0.0050% by mass or more, 0.0070% by mass or more, 0.0010% by mass or more, 0.0030% by mass or more, 0.0050% by mass or more, 0.0070% by mass or more, from the viewpoint of easily reducing the polishing rate of silicon oxide. It may be 0.010% by mass or more, 0.015% by mass or more, 0.020% by mass or more, or 0.025% by mass or more.
• the content of ether compound A is 10% by mass or less, 5.0% by mass or less, 1.0% by mass or less, less than 1.0% by mass, and 0.70% by mass from the viewpoint of easily stabilizing the polishing rate of silicon oxide. % or less, 0.50 mass% or less, less than 0.50 mass%, 0.40 mass% or less, less than 0.40 mass%, 0.30 mass% or less, 0.20 mass% or less, 0.10 mass%
• the content may be less than 0.10 mass%, 0.070 mass% or less, 0.050 mass% or less, less than 0.050 mass%, 0.030 mass% or less, or 0.025 mass% or less. From these viewpoints, the content of ether compound A may be 0.0010 to 10% by mass.
• the content of ether compound A may be in the following range with respect to 100 parts by mass of abrasive grains.
• the content of the ether compound A is 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, more than 1 part by mass, 3 parts by mass or more, 5 parts by mass or more, from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the amount may be at least 7 parts by mass, or at least 10 parts by mass.
• the content of the ether compound A is 200 parts by mass or less, 150 parts by mass or less, 100 parts by mass or less, 70 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, The amount may be less than 40 parts by weight, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less. From these viewpoints, the content of ether compound A may be 0.1 to 200 parts by mass.
• the polishing liquid according to this embodiment may contain components other than abrasive grains, ether compound A, and water.
• components include ether compounds other than ether compound A (hereinafter referred to as ether compound B), nitrogen-containing compounds, acid components, oxidizing agents, quaternary ammonium salts, surfactants, chelating agents, and the like.
• ether compound B ether compounds other than ether compound A
• nitrogen-containing compounds nitrogen-containing compounds
• acid components oxidizing agents, quaternary ammonium salts, surfactants, chelating agents, and the like.
• the polishing liquid according to this embodiment does not need to contain at least one of these components.
• the polishing liquid according to this embodiment may contain ether compound B.
• the ether compound B include polyether compounds.
• polyether compounds include polyglycerin, polysaccharides (for example, dextrin), polyalkylene glycol, polyoxypropylene polyglyceryl ether, polyoxyethylene polyglyceryl ether, 1,4-di(2-hydroxyethoxy)benzene, 2,2- Bis(4-polyoxyethyleneoxyphenyl)propane, 2,2-bis(4-polyoxypropyleneoxyphenyl)propane, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, polyoxyalkylene monophenyl ether, propylene glycol monophenyl Examples include ether, polyoxypropylene monomethyl phenyl ether, polyethylene glycol monomethyl ether, pentaerythritol polyoxyethylene ether, ethylene glycol monoallyl ether, polyoxyethylene monoallyl ether, and alkyl glucoside.
• the content of the ether compound B may be in the following range based on the total mass of the polishing liquid. From the viewpoint of easily stabilizing the polishing rate of silicon oxide, the content of the ether compound B is 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. The content may be 0.08% by mass or more, 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, or 0.35% by mass or more. The content of the ether compound B is 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, and 0.8% by mass, from the viewpoint of easily stabilizing the polishing rate of silicon oxide. The content may be below 0.6% by mass, below 0.5% by mass, or below 0.4% by mass. From these viewpoints, the content of ether compound B may be 0.001 to 5% by mass.
• the polishing liquid according to the present embodiment may contain a nitrogen-containing compound (excluding compounds corresponding to ether compound A, ether compound B, oxidizing agent, quaternary ammonium salt, surfactant, and chelating agent).
• a nitrogen-containing compound means a compound containing one or more nitrogen atoms in the molecule. Examples of nitrogen-containing compounds include amino acids, pyridine compounds, pyrazole compounds, triazole compounds, pyrimidine compounds, imidazole compounds, and the like.
• Amino acids include alanine ( ⁇ -alanine, ⁇ -alanine), arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, Examples include tyrosine and valine.
• pyridine compound examples include pyridine, methylpyridine, acetylpyridine, pyridineamide (nicotinamide), aminopyridine, and the like.
• pyrazole compounds include pyrazole, N-methylpyrazole, 3,5-dimethylpyrazole, 1-allyl-3,5-dimethylpyrazole, 3,5-di(2-pyridyl)pyrazole, 3,5-diisopropylpyrazole, 3 , 5-dimethyl-1-hydroxymethylpyrazole, 3,5-dimethyl-1-phenylpyrazole, 4-methylpyrazole and the like.
• pyrimidine compounds include pyrimidine, 1,3-diphenyl-pyrimidine-2,4,6-trione, 1,4,5,6-tetrahydropyrimidine, 2,4,5-trihydroxypyrimidine, 2,4,6- Examples include trichloropyrimidine, 2,4,6-trimethoxypyrimidine, 2,4,6-triphenylpyrimidine and the like.
• Imidazole compounds include imidazole, 1,1'-carbonylbis-1H-imidazole, 1,1'-oxalyldiimidazole, 1,2,4,5-tetramethylimidazole, 1,2-dimethyl-5-nitroimidazole. , 1,2-dimethylimidazole, 1-butylimidazole, 1-ethylimidazole, 1-methylimidazole, benzimidazole and the like.
• the nitrogen-containing compound may contain at least one selected from the group consisting of amino acids, pyridine compounds, and pyrazole compounds, and may include ⁇ -alanine, pyridine amide, and 3,5- It may contain at least one selected from the group consisting of dimethylpyrazole.
• the content of the nitrogen-containing compound may be in the following range based on the total mass of the polishing liquid. From the viewpoint of easily stabilizing the polishing rate of silicon oxide, the content of the nitrogen-containing compound is 0.0001% by mass or more, 0.0005% by mass or more, 0.001% by mass or more, 0.003% by mass or more, or It may be 0.005% by mass or more. The content of the nitrogen-containing compound is 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less, 0.08% by mass or less, 0.05% by mass from the viewpoint of easily stabilizing the polishing rate of silicon oxide. % or less, 0.03% by mass or less, 0.01% by mass or less, 0.008% by mass or less, or 0.006% by mass or less. From these viewpoints, the content of the nitrogen-containing compound may be 0.0001 to 1% by mass.
• the polishing liquid according to this embodiment may contain an acid component.
• the polishing liquid according to this embodiment may contain an organic acid component or an inorganic acid component as an acid component.
• organic acid components include organic acids (excluding amino acids), organic acid esters, organic acid salts, amino acids, and the like.
• organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-Methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, 3-methylphthalic acid, 4-methylphthalic acid, 3-aminophthalic acid Acid, 4-aminophthalic acid, 3-nitrophthalic acid, 4-nitrophthalic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, is
• organic acid ester examples include esters of the above-mentioned organic acids.
• organic acid salts include ammonium salts, alkali metal salts, alkaline earth metal salts, halides, and the like of the above-mentioned organic acids.
• Examples of the inorganic acid component include inorganic acids, ammonium salts of inorganic acids, chromic acid, and the like.
• Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and the like.
• Examples of ammonium salts of inorganic acids include ammonium salts of monovalent inorganic acids such as ammonium nitrate, ammonium chloride, and ammonium bromide; ammonium salts of divalent inorganic acids such as ammonium carbonate, ammonium sulfate, and ammonium persulfate; ammonium phosphate, boron; Examples include ammonium salts of trivalent inorganic acids such as ammonium acid.
• the content of the acid component may be in the following range based on the total mass of the polishing liquid.
• the content of the acid component is 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 from the viewpoint of easily stabilizing the polishing rate of silicon oxide. mass% or more, 0.06 mass% or more, 0.07 mass% or more, 0.08 mass% or more, 0.09 mass% or more, 0.1 mass% or more, or 0.11 mass% or more good.
• the content of the acid component is 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, and 0.8% by mass or less. , 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, 0.2% by mass or less, or 0.15% by mass or less. From these viewpoints, the content of the acid component may be 0.001 to 5% by mass.
• the polishing liquid according to the present embodiment may contain an oxidizing agent or may not contain an oxidizing agent (the content of the oxidizing agent may be substantially 0% by mass based on the total mass of the polishing liquid). good).
• Oxidizing agents include hydrogen peroxide, peroxide, nitrate, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, persulfate, dichromium. Examples include acid salts, permanganates, ozonated water, silver (II) salts, iron (III) salts, and the like.
• the content of the oxidizing agent may be less than 0.01 mol based on 1 L of polishing liquid.
• the polishing liquid according to the present embodiment may contain a quaternary ammonium salt or may not contain a quaternary ammonium salt (the content of the quaternary ammonium salt is substantially equal to the total mass of the polishing liquid). 0% by mass).
• the quaternary ammonium salt include tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, and tetrapentylammonium salt.
• the content of the quaternary ammonium salt may be less than 0.00001% by mass based on the total mass of the polishing liquid.
• the polishing liquid according to the present embodiment may contain a surfactant or may not contain a surfactant (the content of the surfactant is substantially 0% by mass based on the total mass of the polishing liquid). ).
• the surfactant include decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, dodecylnaphthalenesulfonic acid, and tetradecylnaphthalenesulfonic acid.
• the content of the surfactant may be less than 0.001 g based on 1 L of polishing liquid.
• the polishing liquid according to the present embodiment may contain a chelating agent or may not contain a chelating agent (the content of the chelating agent is substantially 0% by mass based on the total mass of the polishing liquid). good).
• Chelating agents include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenesulfonic acid, transcyclohexanediaminetetraacetic acid.
• 1,2-diaminopropanetetraacetic acid 1,2-diaminopropanetetraacetic acid, ethylenediamineorthohydroxyphenylacetic acid, ethylenediaminedisuccinic acid (SS form), N-(2-carboxylate ethyl)-L-aspartic acid, ⁇ -alaninediacetic acid, 2-phosphonobutane-1 , 2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, 1,2-dihydroxybenzene-4 , 6-disulfonic acid and the like.
• the content of the chelating agent may be less than 0.0003 mol based on 1 L of polishing liquid.
• the polishing liquid according to this embodiment contains water. Water may be contained as the remainder after other constituent components are removed from the polishing liquid.
• the content of water may be in the following range based on the total mass of the polishing liquid.
• the water content is 90.0% by mass or more, 93.0% by mass or more, 95.0% by mass or more, 97.0% by mass or more, 99.0% by mass or more, 99.2% by mass or more, 99.0% by mass or more. It may be 4% by mass or more, 99.5% by mass or more, 99.6% by mass or more, or 99.7% by mass or more.
• the water content may be less than 100% by weight, 99.9% by weight or less, 99.8% by weight or less, or 99.7% by weight or less. From these viewpoints, the content of water may be 90.0% by mass or more and less than 100% by mass.
• the pH of the polishing liquid according to the present embodiment may be in the following range from the viewpoint of easily reducing the polishing rate of silicon oxide.
• the pH of the polishing liquid is 2.0 or higher, 2.5 or higher, 2.5 or higher, 2.6 or higher, 2.7 or higher, 2.8 or higher, 2.9 or higher, 3.0 or higher, or 3.0 or higher. , or 3.1 or more.
• the pH of the polishing liquid is 5.0 or less, less than 5.0, 4.5 or less, 4.0 or less, less than 4.0, 3.8 or less, 3.6 or less, 3.5 or less, less than 3.5 , 3.4 or less, or 3.3 or less. From these viewpoints, the pH of the polishing liquid may be 2.0 to 5.0.
• the pH of the polishing liquid is 2.0 or more, 2.5 or more, 3.0 or more, 3.1 or more, 3.2 or more, 3.3 or more. , 3.4 or more, 3.5 or more, 3.6 or more, 3.7 or more, 3.8 or more, 3.9 or more, or 4.0 or more, and 5.0 or less, 4.9 or less , 4.8 or less, 4.7 or less, 4.6 or less, 4.5 or less, 4.4 or less, 4.3 or less, 4.2 or less, 4.1 or less, or 4.0 or less .
• the pH of the polishing liquid according to the present embodiment can be measured with a pH meter (for example, model number: PHL-40 manufactured by DKK Toa Co., Ltd.). For example, after calibrating a pH meter at two points using phthalate pH buffer (pH: 4.01) and neutral phosphate pH buffer (pH: 6.86) as standard buffer solutions, Place the electrode in the polishing liquid and measure the value after it has stabilized for 2 minutes or more. At this time, the liquid temperatures of the standard buffer solution and polishing solution are both 25°C.
• the polishing liquid according to this embodiment may be stored as a one-component polishing liquid containing at least abrasive grains, ether compound A, and water.
• the one-component polishing liquid may be stored as a storage liquid for polishing liquid with a reduced water content, and may be diluted with water and used immediately before or during polishing.
• the method of supplying the polishing liquid onto the polishing surface plate is by directly feeding the polishing liquid; by feeding the storage liquid for the polishing liquid and water through separate pipes; A method of supplying these by combining and mixing them; a method of mixing the storage liquid for polishing liquid and water in advance and supplying the same, etc. can be used.
• the polishing liquid according to this embodiment is a multi-liquid (for example, two-liquid) polishing liquid set (for example, a polishing liquid set for CMP), which includes a first liquid (slurry) and a second liquid (additive liquid).
• the constituent components of the polishing liquid may be stored separately into a first liquid and a second liquid so that they can be mixed to form the above-mentioned polishing liquid.
• the first liquid includes, for example, at least abrasive grains and water.
• the second liquid contains, for example, at least ether compound A and water.
• the constituent components of the polishing liquid may be stored as a polishing liquid set divided into three or more parts.
• the multi-liquid type polishing liquid set may be stored as a slurry storage liquid and an additive liquid storage liquid with reduced water content, and may also be diluted with water and used immediately before or during polishing.
• the polishing speed can be adjusted by arbitrarily changing the composition of each liquid.
• a method in which the first liquid and the second liquid are sent through separate pipes, and these pipes are combined and mixed to supply A method of supplying by combining and mixing them; a method of supplying by mixing the first and second liquids in advance; a method of mixing the slurry storage liquid, additive liquid storage liquid, and water in advance; It is possible to use a method of supplying the liquid in advance.
• the first liquid and the second liquid in the polishing liquid set are respectively supplied onto the polishing surface plate.
• the surface to be polished is polished using a polishing liquid obtained by mixing the first liquid and the second liquid on a polishing surface plate.
• the polishing method according to the present embodiment may include a polishing step of polishing the surface to be polished using a one-component polishing liquid, in which the first liquid and the second liquid in the polishing liquid set are mixed.
• the method may include a polishing step of polishing the surface to be polished using the resulting polishing liquid.
• the polishing method according to the present embodiment is, for example, a method of polishing a substrate having a surface to be polished.
• the polishing method according to the present embodiment polishes the surface to be polished using the polishing liquid according to the present embodiment.
• the surface to be polished may include silicon oxide, and may include silicon oxide derived from TEOS.
• the material to be polished having the surface to be polished may be a single material or a plurality of materials.
• the material to be polished may be in the form of a film (film to be polished), may be a silicon oxide film, or may be a TEOS film.
• the polishing method according to this embodiment may be a method of polishing a substrate having a surface to be polished containing silicon nitride.
• the polishing method according to this embodiment may be a method of polishing a substrate having a surface to be polished containing silicon oxide and silicon nitride.
• a polishing liquid is supplied between the surface to be polished and the polishing pad while the surface to be polished of the substrate having the surface to be polished is pressed against a polishing pad (polishing cloth) of a polishing surface plate, The surface to be polished is polished by relatively moving the base and the polishing surface plate.
• the polishing step for example, at least a portion of the material to be polished is removed by polishing.
• the substrate to be polished includes, for example, a substrate in which a material to be polished is formed on a substrate related to the manufacture of semiconductor elements (for example, a semiconductor substrate on which an STI pattern, a gate pattern, a wiring pattern, etc. are formed).
• the material to be polished include insulating materials such as silicon oxide; stopper materials such as silicon nitride and polysilicon.
• the material to be polished may be a single material or a plurality of materials. When multiple materials are exposed on the surface to be polished, they can be considered as materials to be polished.
• the material to be polished may be in the form of a film (film to be polished).
• the shape of the insulating member is not particularly limited, and is, for example, film-like (insulating film).
• the shape of the stopper is not particularly limited, and is, for example, film-like (stopper film: silicon nitride film, polysilicon film, etc.).
• the surface of the material to be polished can be improved. It is possible to eliminate unevenness and obtain a smooth surface over the entire surface to be polished.
• a base Polishing an insulating member (a base having an insulating member (e.g., a silicon oxide film containing silicon oxide on at least the surface), a stopper disposed below the insulating member, and a semiconductor substrate disposed below the stopper).
• the stopper material constituting the stopper is, for example, a material whose polishing rate is lower than that of an insulating material, and examples thereof include silicon nitride, polysilicon, and the like.
• the polishing device is a general polishing device having a holder capable of holding a substrate (such as a semiconductor substrate) having a surface to be polished, and a polishing surface plate to which a polishing pad can be attached.
• a substrate such as a semiconductor substrate
• a polishing surface plate to which a polishing pad can be attached.
• Each of the holder and polishing surface plate is equipped with a motor or the like whose rotation speed can be changed.
• a polishing device Mirra 3400 manufactured by APPLIED MATERIALS can be used.
• polishing pad common nonwoven fabrics, foams, non-foams, etc.
• Materials for the polishing pad include polyurethane, acrylic resin, polyester, acrylic-ester copolymer, polytetrafluoroethylene, polypropylene, polyethylene, poly4-methylpentene, cellulose, cellulose ester, polyamide (for example, nylon (trade name)).
• Resins such as polyimide, polyimide amide, polysiloxane copolymer, oxirane compound, phenol resin, polystyrene, polycarbonate, and epoxy resin can be used.
• the material of the polishing pad may be foamed polyurethane or non-foamed polyurethane from the viewpoint of better flatness.
• the polishing pad may be provided with grooves for collecting polishing liquid.
• polishing liquid may be continuously supplied to the polishing pad using a pump or the like. There is no limit to the amount of supply, but the surface of the polishing pad may always be covered with the polishing liquid.
• the substrate after polishing be thoroughly washed under running water to remove particles attached to the substrate.
• dilute hydrofluoric acid or aqueous ammonia may be used for cleaning, and a brush may be used to improve cleaning efficiency.
• a brush may be used to improve cleaning efficiency.
• wipe off water droplets adhering to the substrate using a spin dryer or the like, and then dry the substrate.
• the component manufacturing method according to the present embodiment includes a component manufacturing step of obtaining a component using a substrate (object to be polished) polished by the polishing method according to the present embodiment.
• the component according to the present embodiment is a component obtained by the component manufacturing method according to the present 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). good.
• an electronic component is obtained using a substrate polished by the polishing method according to the present embodiment.
• a semiconductor component for example, a semiconductor package
• the component manufacturing method according to the present embodiment may include a polishing step of polishing the base by the polishing method according to the present embodiment before the component manufacturing step.
• the component manufacturing method according to the present embodiment may include, as one aspect of the component manufacturing step, a singulation step of singulating the base body (object to be polished) polished by the polishing method according to the present embodiment.
• the singulation process may be, for example, a process of obtaining chips (for example, semiconductor chips) by dicing a wafer (for example, a semiconductor wafer) polished by the polishing method according to the present embodiment.
• the method for manufacturing an electronic component according to the present embodiment includes singulating electronic components (for example, semiconductor (parts).
• the method for manufacturing a semiconductor component according to the present embodiment includes dividing a substrate polished by the polishing method according to the present embodiment into individual pieces, such as a semiconductor component (for example, a semiconductor component). package).
• a semiconductor component for example, a semiconductor component. package
• the component manufacturing method according to the present embodiment connects (for example, electrically connection).
• the connected object to be connected to the base body polished by the polishing method according to the present embodiment is not particularly limited, and may be a base body polished by the polishing method according to the present embodiment.
• the connected object may be different from the base polished by the polishing method.
• the substrate and the object to be connected may be connected directly (connected while the substrate and the object to be connected are in contact), or the substrate and the object to be connected may be connected through another member (such as a conductive member). You may do so.
• the connection process can be performed before the singulation process, after the singulation process, or before and after the singulation process.
• the connecting step may be a step of connecting the polished surface of the substrate polished by the polishing method according to the present embodiment and the object to be connected, and the connecting step of the substrate polished by the polishing method according to the present embodiment It may be a step of connecting the surface and the connection surface of the object to be connected.
• the connection surface of the base body may be a polished surface polished by the polishing method according to the present embodiment.
• a connecting body including a base and a connected body can be obtained.
• the connection step when the connection surface of the base body has a metal part, the object to be connected may be brought into contact with the metal part.
• the connection step when the connection surface of the base body has a metal portion and the connection surface of the object to be connected has a metal portion, the metal portions may be brought into contact with each other.
• the metal portion may include copper.
• the device according to the present embodiment (for example, an electronic device such as a semiconductor device) includes a substrate polished by the polishing method according to the present embodiment, and at least one type selected from the group consisting of the parts according to the present embodiment.
• a polishing liquid containing 0.25% by mass of colloidal ceria particles (abrasive grains) and 0.025% by mass of additives was obtained.
• aqueous ammonia was added to adjust the pH.
• the pH of the polishing liquids of Examples 1 and 2 was measured using a pH meter (manufactured by DKK Toa Co., Ltd., model number: PHL-40). After calibrating the pH meter at two points using phthalate pH buffer (pH: 4.01) and neutral phosphate pH buffer (pH: 6.86) as standard buffer solutions, the electrodes of the pH meter were It was placed in a polishing liquid and the value was measured after it stabilized for 2 minutes or more.
• the pH of the polishing liquid of Example 1 is 3.26
• the pH of the polishing liquid of Example 2 is 3.19
• the pH of the polishing liquid of Example 3 is 4.00
• the pH of the polishing liquid of Example 4 is The pH of the liquid was 4.54.
• a film to be polished (silicon oxide film (TEOS film) or silicon nitride film) formed on a ⁇ 200 mm silicon wafer is placed on a holder for attaching a substrate to which a suction pad is attached.
• a substrate having a film (SiN film) was set.
• a holder was placed on a surface plate to which a porous urethane resin pad was attached so that the film to be polished faced the pad.
• polishing liquids While each of the above polishing liquids was supplied onto the pad at a supply rate of 200 mL/min, the substrate was pressed against the pad under a polishing load of 20 kPa. At this time, polishing was performed by rotating the surface plate at 93 min -1 and the holder at 87 min -1 for 30 seconds. The polished substrate was thoroughly washed with pure water and then dried.
• a polishing rate (TEOS RR and SiN RR, unit: ⁇ /min) was determined by measuring the change in the thickness of the film to be polished before and after polishing using an optical interference film thickness measuring device.
• the polishing rate ratio of silicon oxide to silicon nitride (silicon oxide polishing rate/silicon nitride polishing rate) was determined. The results are shown in Table 1.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Mechanical Treatment Of Semiconductor (AREA)
• Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

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• 2023
  • 2023-08-08 JP JP2024540492A patent/JPWO2024034618A1/ja active Pending
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  • 2023-08-08 WO PCT/JP2023/028988 patent/WO2024034618A1/ja not_active Ceased
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