WO2024089919A1 - 砥粒を得るための原料及びその選定方法、砥粒の製造方法、研磨液の製造方法、研磨方法、部品の製造方法、並びに、半導体部品の製造方法 - Google Patents
砥粒を得るための原料及びその選定方法、砥粒の製造方法、研磨液の製造方法、研磨方法、部品の製造方法、並びに、半導体部品の製造方法 Download PDFInfo
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- WO2024089919A1 WO2024089919A1 PCT/JP2023/017463 JP2023017463W WO2024089919A1 WO 2024089919 A1 WO2024089919 A1 WO 2024089919A1 JP 2023017463 W JP2023017463 W JP 2023017463W WO 2024089919 A1 WO2024089919 A1 WO 2024089919A1
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- raw material
- polishing
- abrasive grains
- polished
- cerium
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Classifications
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- 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
- C09K3/1463—Aqueous liquid suspensions
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- 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
-
- 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
- C09K3/1409—Abrasive particles per se
-
- 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
- C09K3/1409—Abrasive particles per se
- C09K3/1418—Abrasive particles per se obtained by division of a mass agglomerated by sintering
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/36—Measuring spectral distribution of X-rays or of nuclear radiation spectrometry
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
-
- 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
- C09K3/1436—Composite particles, e.g. coated particles
Definitions
- This disclosure relates to raw materials for obtaining abrasive grains and methods for selecting them, methods for manufacturing abrasive grains, methods for manufacturing polishing liquids, polishing methods, methods for manufacturing parts, methods for manufacturing semiconductor parts, etc.
- CMP Chemical Mechanical Polishing
- STI shallow trench isolation
- Known polishing solutions used in CMP include those containing abrasive grains containing cerium (see, for example, Patent Documents 1 and 2 below).
- the abrasive grains used in the polishing liquid can be obtained by subjecting the raw material used to obtain the abrasive grains to processing such as crushing.
- processing such as crushing.
- polishing liquids containing abrasive grains there are cases where it is required to increase the polishing speed of silicon oxide on blanket wafers that do not have a pattern.
- One aspect of the present disclosure is to provide a method for selecting a raw material for obtaining abrasive grains, the raw material being capable of adjusting the polishing rate of a material to be polished when the material to be polished is polished using the abrasive grains.
- Another aspect of the present disclosure is to provide a raw material from which abrasive grains can be obtained that have a high polishing rate for silicon oxide on a blanket wafer.
- Another aspect of the present disclosure is to provide a method for manufacturing abrasive grains using the raw material.
- Another aspect of the present disclosure is to provide a method for manufacturing a polishing liquid using the abrasive grains obtained by the method for manufacturing abrasive grains.
- the present disclosure relates in some aspects to the following items [1] to [13] etc.
- [1] A method for selecting a raw material for obtaining abrasive grains, the raw material containing cerium, the raw material being selected based on an average value of a positron lifetime measured by a positron annihilation method.
- [2] The method for selecting a raw material according to [1], wherein the raw material contains cerium oxide.
- the raw material according to [3] which contains cerium oxide.
- [5] The raw material according to [3] or [4], containing cerium oxide derived from cerium oxycarbonate.
- [6] The raw material according to any one of [3] to [5], containing cerium oxide derived from cerium carbonate.
- [7] The raw material according to any one of [3] to [6], containing cerium oxide derived from a cerium complex of trimesic acid.
- a method for producing abrasive grains comprising grinding a raw material selected by the raw material selection method described in [1] or [2], or a raw material described in any one of [3] to [7].
- a method for producing a polishing liquid comprising mixing the abrasive grains obtained by the method for producing abrasive grains described in [8] with water.
- a polishing method comprising polishing a workpiece with the polishing liquid obtained by the method for producing a polishing liquid according to [9].
- a method for manufacturing a part comprising obtaining a part using a polished member polished by the polishing method according to [10] or [11].
- a method for producing a semiconductor component comprising obtaining a semiconductor component using a polished member polished by the polishing method according to [10] or [11].
- a method for selecting a raw material for obtaining abrasive grains can be provided, the raw material being capable of adjusting the polishing rate of a material to be polished when the material to be polished is polished using the abrasive grains.
- a raw material can be provided from which abrasive grains having a high polishing rate of silicon oxide on a blanket wafer can be obtained.
- a method for manufacturing abrasive grains using the raw material can be provided.
- a method for manufacturing a polishing liquid using the abrasive grains obtained by the method for manufacturing abrasive grains can be provided.
- a polishing method can be provided using a polishing liquid obtained by the method for manufacturing a polishing liquid.
- a method for manufacturing a part using a polished member polished by the polishing method can be provided.
- a method for manufacturing a semiconductor part using a polished member polished by the polishing method can be provided.
- the numerical range indicated using “ ⁇ ” indicates a range including the numerical values described before and after “ ⁇ ” as the minimum and maximum values, respectively.
- “A or more” in the numerical range means a range exceeding A and A.
- “A or less” in the numerical range means a range less than A and A.
- the upper limit or lower limit of a numerical range of a certain stage can be arbitrarily combined with the upper limit or lower limit of a numerical range of another stage.
- the upper limit or lower limit of the numerical range may be replaced with a value shown in an experimental example.
- “A or B” may include either A or B, or may include both.
- the materials exemplified in this specification may be used alone or in combination of two or more types.
- the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified.
- the term “process” includes not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved.
- “Abrasive grain” refers to a collection of multiple particles, but for convenience, a single particle that makes up an abrasive grain is sometimes called an abrasive grain.
- the raw material and the selection method thereof according to this embodiment are raw materials and a selection method thereof for obtaining abrasive grains (abrasive grains used in polishing liquid).
- the raw material contains cerium.
- the raw material selection method according to this embodiment the raw material is selected based on the average value of the positron lifetime (average positron lifetime) measured by positron annihilation spectroscopy.
- the raw material according to this embodiment has an arbitrary value as the average value (average positron lifetime) of the positron lifetime (positron lifetime of the raw material) measured by positron annihilation spectroscopy, depending on the application.
- the shape of the raw material according to this embodiment is not particularly limited, and may be, for example, particulate, fibrous, flake-like, liquid (e.g., highly viscous liquid), etc.
- the inventors have focused on raw materials containing cerium as raw materials for obtaining abrasive grains by performing a process such as a crushing process, and have found that by adjusting the average value of the positron lifetime of the raw material measured by a positron annihilation method, the polishing speed of the material to be polished when the material to be polished is polished with the abrasive grains can be adjusted.
- the raw materials are selected based on the average value of the positron lifetime measured by a positron annihilation method, and abrasive grains are obtained using such raw materials, so that the polishing speed of the material to be polished when the material to be polished is polished with the abrasive grains can be adjusted.
- the polishing speed of the material to be polished when the material to be polished is polished with the abrasive grains can be adjusted.
- a polishing speed adjustment method can be provided that adjusts the polishing speed of the material to be polished based on the average value of the positron lifetime (the average value of the positron lifetime measured by a positron annihilation method) in the raw materials for obtaining the abrasive grains.
- the polishing speed of the material to be polished on a blanket wafer or a patterned wafer can be adjusted.
- the polishing speed of the material to be polished can be adjusted so as to increase the polishing speed of the material to be polished, and the polishing speed of the material to be polished can also be adjusted so as to decrease the polishing speed of the material to be polished.
- the polishing speed of the insulating material can be adjusted, and the polishing speed of silicon oxide can be adjusted.
- the raw material for obtaining the abrasive grains may contain cerium (cerium element) and may contain a cerium compound.
- cerium compound include cerium oxide, cerium hydroxide, ammonium cerium nitrate, cerium acetate, cerium sulfate (e.g., cerium sulfate hydrate), cerium bromate, cerium bromide, cerium chloride, cerium oxalate, cerium nitrate, and cerium carbonate.
- the raw material for obtaining the abrasive grains may contain cerium oxide from the viewpoint of easily adjusting the polishing speed of the polished material, or from the viewpoint of easily increasing the polishing speed of the polished material (polishing speed of silicon oxide on a blanket wafer, polishing speed of silicon oxide on a patterned wafer, etc.; the same applies below).
- the cerium oxide may be CeO 2 (cerium (IV) oxide, ceria) or Ce 2 O 3 (cerium (III) oxide).
- the raw material for obtaining the abrasive grains may be obtained by oxidizing a cerium source containing cerium.
- the oxidation method include a calcination method in which the cerium source is calcined at 600 to 900°C or the like; and a chemical oxidation method in which the cerium source is oxidized using an oxidizing agent such as hydrogen peroxide.
- the raw material for obtaining the abrasive grains may contain cerium oxide derived from the cerium source, or may contain a calcined product of the cerium source.
- a cerium salt or a cerium complex may be used as the cerium source.
- the raw material for obtaining the abrasive grains may contain cerium oxide derived from a cerium salt, or may contain cerium oxide derived from a cerium complex.
- the cerium complex may include a cerium complex of a compound A having a carbon chain (a complex having a ligand of compound A and cerium) from the viewpoint of easily increasing the polishing speed of the material to be polished.
- Compound A may include at least one selected from the group consisting of a carboxy group and a carboxylate group from the viewpoint of easily increasing the polishing speed of the material to be polished.
- the number of carboxy groups or the total number of carboxy groups and carboxylate groups may be 1 to 4, 1 to 3, 2 to 4, 2 to 3, or 3 to 4 from the viewpoint of easily increasing the polishing speed of the material to be polished.
- Compound A may have at least one selected from the group consisting of a linear (acyclic) carbon chain and a cyclic carbon chain, and may have a cyclic carbon chain, from the viewpoint of easily increasing the polishing speed of the material to be polished.
- the cyclic carbon chain may be an alicyclic ring, a heterocyclic ring, or an aromatic ring.
- Compound A may have an aromatic ring from the viewpoint of easily increasing the polishing speed of the material to be polished.
- the cerium complex may include a cerium complex of an aromatic carboxylic acid, a cerium complex of benzenetricarboxylic acid, or a cerium complex of trimesic acid.
- the cerium complex may include a metal organic framework.
- Cerium sources include cerium carbonate (excluding cerium oxycarbonate), cerium oxycarbonate, cerium complex of trimesic acid, cerium acetate, cerium stearate, cerium nitrate, cerium sulfate, cerium oxalate, cerium hydroxide, etc.
- the raw material for obtaining the abrasive grains may contain at least one selected from the group consisting of cerium oxide derived from cerium carbonate (e.g., calcined product of cerium carbonate), cerium oxide derived from cerium oxycarbonate (e.g., calcined product of cerium oxycarbonate), and cerium oxide derived from a cerium complex of trimesic acid (e.g., calcined product of a cerium complex of trimesic acid).
- cerium oxide derived from cerium carbonate e.g., calcined product of cerium carbonate
- cerium oxide derived from cerium oxycarbonate e.g., calcined product of cerium oxycarbonate
- cerium oxide derived from a cerium complex of trimesic acid e.g., calcined product of a cerium complex of trimesic acid
- the raw material for obtaining the abrasive grains may be in an embodiment containing cerium oxide derived from cerium carbonate, an embodiment containing cerium oxide derived from cerium oxycarbonate, or an embodiment containing cerium oxide derived from a cerium complex of trimesic acid.
- positron lifetime is the component derived from the sample when a three-component analysis is performed using two components, Kapton and adhesive, as the radiation source components after measuring the positron lifetime by positron annihilation method.
- the average positron lifetime can be used, for example, as an index of the average size of oxygen defects.
- the average positron lifetime can be measured by the method described in the experimental example below.
- the average positron lifetime can be adjusted by the preparation conditions of the raw materials used to obtain the abrasive grains. For example, the higher the firing temperature of the cerium source, the smaller (shorter) the positron lifetime tends to be.
- the inventors have found that the polishing rate of silicon oxide can be easily increased by using abrasive grains obtained using a raw material having an average positron lifetime of 285 to 360 ps measured by positron annihilation spectroscopy.
- One aspect of the raw material according to this embodiment is a raw material for obtaining abrasive grains, which contains cerium and has an average positron lifetime of 285 to 360 ps measured by positron annihilation spectroscopy. Such a raw material makes it easy to increase the polishing rate of silicon oxide on a blanket wafer.
- a polishing rate of silicon oxide on a blanket wafer of, for example, 50 nm/min or more (preferably, 70 nm/min or more, 90 nm/min or more, 100 nm/min or more, 110 nm/min or more, 120 nm/min or more, etc.) can be obtained.
- the polishing rate of silicon oxide in a patterned wafer can be easily increased.
- the reasons why a high polishing rate is likely to be obtained are not limited to the above. That is, the smaller the average value of the positron lifetime in the raw material for obtaining the abrasive grains, the smaller the oxygen defects inside the raw material, and the smaller the oxygen defects inside the abrasive grains obtained using such raw material. If the oxygen defects inside the abrasive grains are small, the abrasive grains are less likely to break during polishing, and it is easier to obtain sufficient mechanical polishing power of the abrasive grains.
- the larger the average value of the positron lifetime in the raw material for obtaining the abrasive grains the larger the oxygen defects inside the raw material, and the larger the oxygen defects inside the abrasive grains obtained using such raw material. If the oxygen defects inside the abrasive grains are large, the abrasive grains are more likely to break during polishing, but it is easier to obtain sufficient chemical polishing power of the abrasive grains. Therefore, when the average value of the positron lifetime is within a specific range, it is easier to obtain a high polishing rate by obtaining sufficient mechanical polishing power and chemical polishing power.
- the raw material selection method includes a selection process for selecting raw materials (raw materials for obtaining abrasive grains) based on the average value of the positron lifetime measured by positron annihilation spectroscopy.
- raw materials may be selected based on whether the average value of the positron lifetime is within any of the following ranges (for example, whether the average value of the positron lifetime is 285 to 360 ps).
- the average positron lifetime (the positron lifetime of the raw material) measured by positron annihilation may be in the following ranges from the viewpoint of easily adjusting the polishing speed of the material to be polished.
- the average positron lifetime may be 200 ps or more, 250 ps or more, or 280 ps or more.
- the average positron lifetime may be 500 ps or less, 450 ps or less, 400 ps or less, 390 ps or less, 380 ps or less, or 370 ps or less.
- the average positron lifetime (positron lifetime of the raw material) measured by positron annihilation may be in the following ranges from the viewpoint of easily adjusting the polishing speed of the material to be polished or from the viewpoint of easily increasing the polishing speed of the material to be polished (polishing speed of silicon oxide on a blanket wafer, polishing speed of silicon oxide on a patterned wafer, etc.).
- the average positron lifetime may be 285 ps or more, 290 ps or more, 295 ps or more, 300 ps or more, 305 ps or more, 310 ps or more, 315 ps or more, 320 ps or more, 325 ps or more, or 330 ps or more.
- the average positron lifetime may be 360 ps or less, 355 ps or less, 350 ps or less, 345 ps or less, 340 ps or less, 335 ps or less, 330 ps or less, 325 ps or less, 320 ps or less, 315 ps or less, 310 ps or less, 305 ps or less, 300 ps or less, or 295 ps or less.
- the average positron lifetime may be 200-500ps, 200-360ps, 200-330ps, 200-300ps, 285-500ps, 285-360ps, 285-330ps, 285-300ps, 300-500ps, 300-360ps, 300-330ps, 330-500ps, 330-360ps, or 360-500ps.
- the abrasive grains and the manufacturing method thereof according to the present embodiment are abrasive grains containing cerium and a manufacturing method thereof.
- the abrasive grains may be obtained by processing the raw material according to the present embodiment, for example, by crushing the raw material according to the present embodiment.
- the abrasive grains may be obtained by processing the raw material selected by the raw material selection method according to the present embodiment, for example, by crushing the raw material selected by the raw material selection method according to the present embodiment.
- the abrasive grains according to the present embodiment may be abrasive grains obtained by processing the raw material according to the present embodiment (abrasive grains obtained by the manufacturing method of the abrasive grains according to the present embodiment), for example, by crushing the raw material according to the present embodiment.
- the abrasive grains according to the present embodiment may be abrasive grains obtained by processing the raw material selected by the raw material selection method according to the present embodiment, for example, by crushing the raw material selected by the raw material selection method according to the present embodiment.
- the crushed material according to the present embodiment may be a crushed material of the raw material ... a crushed material of the raw material selected by the raw material selection method according to the present embodiment.
- the abrasive grains may contain cerium (cerium element) and may contain a cerium compound.
- the cerium compound include cerium oxide, cerium hydroxide, ammonium cerium nitrate, cerium acetate, cerium sulfate (e.g., cerium sulfate hydrate), cerium bromate, cerium bromide, cerium chloride, cerium oxalate, cerium nitrate, and cerium carbonate.
- the abrasive grains may contain cerium oxide from the viewpoint of easily increasing the polishing rate of the material to be polished.
- the cerium oxide may be CeO2 (cerium (IV) oxide, ceria) or Ce2O3 (cerium (III) oxide).
- the method for manufacturing the abrasive grains according to the present embodiment may include a processing step for processing the raw material according to the present embodiment, for example, a crushing step for obtaining a crushed product by crushing the raw material according to the present embodiment.
- the method for manufacturing the abrasive grains according to the present embodiment may include a processing step for processing the raw material selected by the raw material selection method according to the present embodiment, for example, a crushing step for obtaining a crushed product by crushing the raw material selected by the raw material selection method according to the present embodiment.
- the method for manufacturing the abrasive grains according to the present embodiment may include a classification step for classifying the crushed product after the crushing step. In the classification step, coarse objects (e.g., coarse particles) can be removed.
- the crushing method in the crushing step is not particularly limited, and various crushing methods such as wet crushing and dry crushing can be used.
- the classification method in the classification step is not particularly limited, and examples thereof include centrifugation.
- the polishing liquid according to this embodiment contains the abrasive grains according to this embodiment and water.
- the polishing liquid according to this embodiment may contain, in addition to the abrasive grains and water, components other than the abrasive grains and water (for example, various components described later).
- the multiple-liquid polishing liquid according to this embodiment includes liquid A (first liquid) containing the abrasive grains according to this embodiment and water, and liquid B (second liquid) containing components other than the abrasive grains and water (for example, various components described later) and water.
- Liquid A may contain components other than the abrasive grains and water (for example, various components described later), or may not contain components other than the abrasive grains and water (for example, various components described later).
- the polishing liquid may be obtained by mixing the abrasive grains according to this embodiment (for example, abrasive grains obtained by the method for producing abrasive grains according to this embodiment) with water, and the polishing liquid may be obtained by mixing liquid A and liquid B of the multiple-liquid polishing liquid according to this embodiment with each other.
- Liquid A can be obtained by mixing the abrasive grains according to this embodiment (for example, abrasive grains obtained by the method for producing abrasive grains according to this embodiment) with water.
- Liquid A may be multiple liquids, for example multiple liquids with different types of abrasive grains.
- Liquid B may be multiple liquids, for example multiple liquids with different types of components other than abrasive grains and water.
- the content of abrasive grains may be within the following ranges based on the total mass of the polishing liquid or the total mass of water. From the viewpoint of easily increasing the polishing rate of the material being polished, the content of abrasive grains may be 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, 0.2 mass% or more, 0.3 mass% or more, 0.4 mass% or more, or 0.5 mass% or more.
- the content of the abrasive grains may be 10% by mass or less, 8% 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, or 0.5% by mass or less, from the viewpoint of easily suppressing an increase in the viscosity of the polishing liquid, aggregation of the abrasive grains, etc. From these viewpoints, the content of the abrasive grains may be 0.01 to 10% by mass, 0.01 to 5% by mass, 0.01 to 1% by mass, 0.05 to 10% by mass, 0.05 to 5% by mass, 0.05 to 1% by mass, 0.1 to 10% by mass, 0.1 to 5% by mass, or 0.1 to 1% by mass.
- Water may be contained as the remainder after removing other components from the polishing liquid.
- the water content may be in the following ranges based on the total mass of the polishing liquid.
- the water content may be 90 mass% or more, 91 mass% or more, 92 mass% or more, 93 mass% or more, 94 mass% or more, 95 mass% or more, 96 mass% or more, 97 mass% or more, 98 mass% or more, or 99 mass% or more.
- the water content may be less than 100 mass%, 99.9 mass% or less, 99.8 mass% or less, 99.7 mass% or less, 99.6 mass% or less, or 99.5 mass% or less. From these perspectives, the water content may be 90 mass% or more and less than 100 mass%, 95 mass% or more and less than 100 mass%, or 98 mass% or more and less than 100 mass%.
- the polishing liquid according to this embodiment may contain a phosphate compound as necessary.
- the phosphate compound may be used as a dispersant for the abrasive grains.
- As the phosphate compound at least one selected from the group consisting of phosphates and their derivatives (phosphate derivatives) may be used.
- As the hydrogen phosphate compound at least one selected from the group consisting of hydrogen phosphates and their derivatives (hydrogen phosphate derivatives) may be used.
- Phosphate salts include potassium phosphate salts, sodium phosphate salts, ammonium phosphate salts, calcium phosphate salts, etc., and more specifically, tripotassium phosphate, trisodium phosphate, ammonium phosphate, tricalcium phosphate, etc.
- Phosphate derivatives include sodium diphosphate, potassium diphosphate, potassium polyphosphate, ammonium polyphosphate, calcium polyphosphate, etc.
- hydrogen phosphate salts include potassium hydrogen phosphate salts, sodium hydrogen phosphate salts, ammonium hydrogen phosphate salts, and calcium hydrogen phosphate salts, and more specifically, dipotassium hydrogen phosphate, disodium hydrogen phosphate, diammonium hydrogen phosphate, calcium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, and calcium dihydrogen phosphate.
- hydrogen phosphate salt derivatives include potassium dodecyl hydrogen phosphate, sodium dodecyl hydrogen phosphate, and dodecyl ammonium hydrogen phosphate.
- the polishing liquid according to this embodiment may contain hydrogen phosphate or ammonium dihydrogen phosphate, from the viewpoint of easily increasing the polishing rate of the material to be polished.
- the content of the phosphate compound may be in the following ranges based on the total mass of the polishing liquid or the total mass of water. From the viewpoint of easily increasing the polishing rate of the material to be polished, the content of the phosphate compound may be 0.0001 mass% or more, 0.0005 mass% or more, 0.001 mass% or more, 0.002 mass% or more, 0.003 mass% or more, 0.004 mass% or more, 0.005 mass% or more, 0.008 mass% or more, or 0.01 mass% or more.
- the content of the phosphate compound may be 1 mass% or less, 0.5 mass% or less, 0.1 mass% or less, 0.08 mass% or less, 0.05 mass% or less, 0.04 mass% or less, 0.03 mass% or less, 0.02 mass% or less, or 0.01 mass% or less. From these viewpoints, the content of the phosphate compound may be 0.0001 to 1 mass%, 0.0001 to 0.1 mass%, 0.0001 to 0.05 mass%, 0.001 to 1 mass%, 0.001 to 0.1 mass%, 0.001 to 0.05 mass%, 0.005 to 1 mass%, 0.005 to 0.1 mass%, or 0.005 to 0.05 mass%.
- the content of the phosphate compound may be in the following ranges per 100 parts by mass of abrasive grains. From the viewpoint of easily increasing the polishing rate of the material to be polished, the content of the phosphate compound may be 0.01 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, 0.3 parts by mass or more, 0.5 parts by mass or more, 0.8 parts by mass or more, 1 part by mass or more, 1.2 parts by mass or more, 1.5 parts by mass or more, 1.8 parts by mass or more, or 2 parts by mass or more.
- the content of the phosphate compound may be 50 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 3 parts by mass or less, 2.5 parts by mass or less, or 2 parts by mass or less.
- the content of the phosphate compound may be 0.01 to 50 parts by mass, 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, 0.1 to 50 parts by mass, 0.1 to 10 parts by mass, 0.1 to 5 parts by mass, 0.5 to 50 parts by mass, 0.5 to 10 parts by mass, 0.5 to 5 parts by mass, 1 to 50 parts by mass, 1 to 10 parts by mass, or 1 to 5 parts by mass.
- the polishing liquid according to this embodiment may contain a polymer as necessary.
- the polymer include homopolymers (polyacrylic acid, etc.) of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.; ammonium salts or amine salts of the homopolymers; copolymers of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc.
- alkyl acrylates methyl acrylate, ethyl acrylate, etc.
- hydroxyalkyl acrylates hydroxyethyl acrylate, etc.
- alkyl methacrylates methyl methacrylate, ethyl methacrylate, etc.
- hydroxyalkyl methacrylates hydroxyethyl methacrylate, etc.
- styrene compounds styrene, alkylstyrene, styrenesulfonic acid, etc.
- vinyl acetate and vinyl alcohol
- ammonium salts or amine salts of the copolymers styrene compounds
- the polishing liquid according to this embodiment may contain a copolymer having at least one selected from the group consisting of acrylic acid and methacrylic acid and a styrene compound as monomer units, or a copolymer having styrene and acrylic acid as monomer units (styrene/acrylic acid copolymer).
- the polishing liquid according to this embodiment may contain an acid component (excluding compounds corresponding to phosphate compounds) as necessary.
- acid components include organic acids such as propionic acid and acetic acid (excluding compounds corresponding to amino acids); inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and boric acid; and amino acids such as glycine.
- the polishing liquid according to this embodiment may contain components other than the abrasive grains, water, phosphate compound, polymer, and acid component according to this embodiment.
- Such components are not particularly limited, but may include abrasive grains that do not contain cerium; basic compounds, etc.
- the pH of the polishing liquid in this embodiment may be in the following ranges from the viewpoint of easily increasing the polishing rate of the material being polished.
- the pH of the polishing liquid may be 1.0 or more, 1.5 or more, 2.0 or more, 2.5 or more, 3.0 or more, 3.5 or more, 4.0 or more, 4.5 or more, 5.0 or more, 5.5 or more, 6.0 or more, 6.5 or more, 7.0 or more, more than 7.0, 7.5 or more, 8.0 or more, or 8.5 or more.
- the pH of the polishing liquid may be 12.0 or less, 11.5 or less, 11.0 or less, 10.5 or less, 10.0 or less, 9.5 or less, or 9.0 or less.
- the pH of the polishing liquid may be 1.0 to 12.0, 1.0 to 10.0, 1.0 to 9.0, 5.0 to 12.0, 5.0 to 10.0, 5.0 to 9.0, 7.0 to 12.0, 7.0 to 10.0, or 7.0 to 9.0.
- the pH of the polishing liquid according to this embodiment can be measured by the method described in the experimental example below.
- the polishing method according to this embodiment includes a polishing step of polishing a member to be polished using the polishing liquid according to this embodiment (for example, the polishing liquid obtained by the manufacturing method of the polishing liquid according to this embodiment).
- the polishing liquid used in the polishing step may be a polishing liquid obtained by mixing liquid A (first liquid) and liquid B (second liquid) of the multiple liquid type polishing liquid according to this embodiment.
- the surface to be polished of the member to be polished can be polished.
- at least a part of the material to be polished in the member to be polished can be polished and removed. Examples of the material to be polished include insulating materials such as silicon oxide and silicon nitride.
- the member to be polished may contain silicon oxide, or may contain silicon oxide and silicon nitride.
- a blanket wafer having no pattern may be polished, a pattern area in which linear silicon nitride patterns with a line width of 50 ⁇ m and linear silicon oxide patterns with a line width of 50 ⁇ m are alternately arranged may be polished, or a pattern area in which linear silicon nitride patterns with a line width of 20 ⁇ m and linear silicon oxide patterns with a line width of 80 ⁇ m are alternately arranged may be polished.
- the abrasive grains, polishing liquid, polishing method, etc. according to this embodiment are not limited to being used for polishing these members to be polished, and may be used, for example, for polishing other pattern areas.
- the member to be polished is not particularly limited, and may be a wafer (e.g., a semiconductor wafer) or a chip (e.g., a semiconductor chip).
- the member to be polished may be a wiring board or a circuit board.
- the component manufacturing method according to the present embodiment includes a component manufacturing step of obtaining a component using a member to be 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 the present embodiment is not particularly limited, and may be an electronic component (e.g., a semiconductor component such as a semiconductor package), a wafer (e.g., a semiconductor wafer), or a chip (e.g., a semiconductor chip).
- the electronic component manufacturing method according to the present embodiment obtains an electronic component using a member to be polished by the polishing method according to the present embodiment.
- the semiconductor component manufacturing method according to the present embodiment obtains a semiconductor component (e.g., a semiconductor package) using a member to be polished by the polishing method according to the present embodiment.
- the component manufacturing method according to the present embodiment may include a polishing step of polishing the member to be polished 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 process, a singulation process for singulating the polished member polished by the polishing method according to the present embodiment.
- the singulation process may be, for example, a process for dicing a wafer (e.g., a semiconductor wafer) polished by the polishing method according to the present embodiment to obtain chips (e.g., semiconductor chips).
- the electronic component manufacturing method according to the present embodiment may include a process for singulating the polished member polished by the polishing method according to the present embodiment to obtain electronic components (e.g., semiconductor components).
- the semiconductor component manufacturing method according to the present embodiment may include a process for singulating the polished member polished by the polishing method according to the present embodiment to obtain semiconductor components (e.g., semiconductor packages).
- the manufacturing method of the component according to the present embodiment may include, as one aspect of the component manufacturing process, a connection process for connecting (e.g., electrically connecting) the polished member polished by the polishing method according to the present embodiment to another connected object.
- the connected object to be connected to the polished member polished by the polishing method according to the present embodiment is not particularly limited, and may be the polished member polished by the polishing method according to the present embodiment, or may be a connected object different from the polished member polished by the polishing method according to the present embodiment.
- the polished member and the connected object may be directly connected (connected in a state where the polished member and the connected object are in contact with each other), or the polished member and the connected object may be connected via another member (such as a conductive member).
- the connection process may be performed before the singulation process, after the singulation process, or before or after the singulation process.
- the connecting step may be a step of connecting the polished surface of the polished member polished by the polishing method according to this embodiment to the connected body, or may be a step of connecting the connecting surface of the polished member polished by the polishing method according to this embodiment to the connecting surface of the connected body.
- the connecting surface of the polished member may be the polished surface polished by the polishing method according to this embodiment.
- the connecting step can obtain a connected body including the polished member and the connected body.
- the connecting step if the connecting surface of the polished member has a metal part, the connected body may be brought into contact with the metal part.
- the connecting step if the connecting surface of the polished member has a metal part and the connecting surface of the connected body has a metal part, the metal parts may be brought into contact with each other.
- the metal part may contain, for example, copper.
- the device according to this embodiment (e.g., an electronic device such as a semiconductor device) comprises a polished member polished by the polishing method according to this embodiment, and at least one selected from the group consisting of the parts according to this embodiment.
- cerium oxide particles The cerium source shown in Table 1 was calcined in air at 800° C. for 1 hour using an electric furnace to obtain cerium oxide particles (ceria particles).
- the cerium complex of trimesic acid was prepared by the following procedure. First, a trimesic acid solution was prepared by adding 34.7 g (165 mmol) of trimesic acid (1,3,5-BTC: 1,3,5-Benzene tricarboxylic acid, manufactured by Tokyo Chemical Industry Co., Ltd.) to 480 mL of a water/ethanol mixed solvent (mass ratio 1:1). In addition, an aqueous cerium nitrate solution was prepared by adding 71.2 g (164 mmol) of cerium nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to 20 mL of water.
- mixed solution A After obtaining mixed solution A by adding the above-mentioned aqueous cerium nitrate solution to the above-mentioned trimesic acid solution, mixed solution A was stirred at 25 ° C. and 400 rpm for 5 hours using a magnetic stirrer. After solid content (white precipitate) was generated in mixed solution A, mixed solution A was left to stand for 15 hours. After the solid content was redispersed by stirring the mixed solution A, the mixed solution A was placed in a 50 mL centrifuge tube and centrifuged at 5000 rpm for 5 minutes.
- the above-mentioned cerium oxide particles were filled to a height of 5 mm in a powder measurement cell, and the positron lifetime (positron annihilation lifetime) was measured under the following conditions using the positron annihilation method.
- positron lifetime positron annihilation lifetime
- a three-component analysis was performed, including the lifetime and strength of the Kapton and adhesive contained in the radiation source.
- the lifetime ⁇ 1 of the Kapton contained in the radiation source is known to be 0.38 ns, which is close to the positron lifetime of the sample, so in order to correctly measure the positron lifetime of the sample, it is necessary to fix the intensity I1 of the Kapton contained in the radiation source. Since I1 is known to be about 20 to 35%, it was fixed at 30% in this measurement.
- ⁇ 2 is the lifetime of the adhesive contained in the radiation source, and I2, which corresponds to this lifetime, indicates the strength of the adhesive contained in the radiation source.
- Measuring device Product name "PSA Type L-II” manufactured by Toyo Seiko Co., Ltd.
- Positron source Thin-film positron source (manufactured by Japan Radioisotope Association) Total count: 1,000,000 counts
- the above suspension was subjected to a dispersion process for 30 minutes using an ultrasonic dispersion device (manufactured by SND Co., Ltd., product name "US-105").
- an ultrasonic dispersion device manufactured by SND Co., Ltd., product name "US-105".
- the cerium oxide particles in the above suspension were ground (wet ground) using a bead mill (manufactured by Ashizawa Finetech Co., Ltd., product name: Labostar Mini, model number: DMS65) until the particle size reached approximately 200 nm.
- a classification process was performed using a centrifuge (manufactured by Eppendorf Himac Technologies Co., Ltd., product name: CF-15R) to remove coarse particles in the above-mentioned suspension and to make the particle size uniform to about 150 nm, thereby obtaining an aqueous dispersion of abrasive grains.
- the classification process was performed by placing 50 g of the suspension in a centrifuge tube and centrifuging at 1500 to 3700 min -1 for 5 minutes.
- the above-mentioned aqueous dispersion was diluted with water to obtain a polishing liquid. Based on the total mass of the polishing liquid, the content of abrasive grains was 0.5 mass% and the content of ammonium dihydrogen phosphate was 0.01 mass%.
- the pH of the polishing solution was measured using a compact pH meter (manufactured by Horiba Ltd., product name: LAQUA twin). After two-point calibration of the pH meter using two types of pH buffer solutions (pH 4.01 and pH 6.86) as standard buffer solutions, the pH meter sensor was placed in the polishing solution, and the pH was measured after the pH had stabilized. The liquid temperatures of both the standard buffer solutions and the polishing solution were 25°C. The measurement results are shown in Table 1.
- a blanket wafer (BKW) was prepared by the following procedure. First, a ⁇ 200 mm patternless wafer having a silicon oxide film (SiO 2 , initial film thickness: 2000 nm) on its surface was prepared. Next, this wafer was cut into 20 mm ⁇ 20 mm to obtain a blanket wafer for polishing.
- SiO 2 silicon oxide film
- a patterned wafer was fabricated by the following procedure. First, a product name "8"SEMATECH864" (Stop on Nitride) manufactured by SEMATECH was prepared. This wafer was obtained by forming a SiN film as a stopper film on a part of a silicon substrate having a diameter of 200 mm, etching the silicon substrate of the part without the SiN film by 350 nm to form a recess, and then forming a 600 nm SiO2 film on the stopper film and in the recess by a plasma CVD method.
- a patterned wafer was obtained having a patterned region in which the line width (L/S; unit ⁇ m) of the SiN pattern (Line) and the SiO2 pattern (Space) is 50/50, and a patterned region in which the line width (L/S; unit ⁇ m) of the SiN pattern (Line) and the SiO2 pattern (Space) is 20/80.
- the above-mentioned wafer (blanket wafer or pattern wafer) was attached to a holder for mounting a substrate to which an adsorption pad was attached.
- the holder was placed on a platen to which a polishing pad (Nitta DuPont Co., Ltd., product name: IC1010) was attached, so that the surface to be polished faced the polishing pad.
- the platen was rotated at 120 min -1 , and the holder was rotated together with the platen to perform polishing for 60 seconds.
- the polished wafer was thoroughly washed with pure water and then dried.
- a film thickness measuring device For blanket wafers, a film thickness measuring device (Toho Technology Co., Ltd., product name: TohoSpec3100) was used to measure the film thickness at a total of five measurement points: the center point of the wafer after polishing and four points 7.1 cm away from the center point in the diagonal direction.
- the polishing rate of the blanket wafer was calculated by taking the difference between the average of these film thicknesses and the film thickness at the center point of the wafer before polishing as the amount of film thickness change. The results are shown in Table 1.
- Table 1 The results are shown in Table 1.
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Abstract
Description
[1]砥粒を得るための原料の選定方法であって、前記原料がセリウムを含み、陽電子消滅法により測定される陽電子寿命の平均値に基づき前記原料を選定する、原料の選定方法。
[2]前記原料がセリウム酸化物を含む、[1]に記載の原料の選定方法。
[3]砥粒を得るための原料であって、セリウムを含み、陽電子消滅法により測定される陽電子寿命の平均値が285~360psである、原料。
[4]セリウム酸化物を含む、[3]に記載の原料。
[5]オキシ炭酸セリウム由来のセリウム酸化物を含む、[3]又は[4]に記載の原料。
[6]炭酸セリウム由来のセリウム酸化物を含む、[3]~[5]のいずれか一つに記載の原料。
[7]トリメシン酸のセリウム錯体由来のセリウム酸化物を含む、[3]~[6]のいずれか一つに記載の原料。
[8][1]又は[2]に記載の原料の選定方法により選定された原料、又は、[3]~[7]のいずれか一つに記載の原料を粉砕する、砥粒の製造方法。
[9][8]に記載の砥粒の製造方法により得られた砥粒と、水と、を混合する、研磨液の製造方法。
[10][9]に記載の研磨液の製造方法により得られた研磨液を用いて被研磨部材を研磨する、研磨方法。
[11]前記被研磨部材が酸化ケイ素を含む、[10]に記載の研磨方法。
[12][10]又は[11]に記載の研磨方法により研磨された被研磨部材を用いて部品を得る、部品の製造方法。
[13][10]又は[11]に記載の研磨方法により研磨された被研磨部材を用いて半導体部品を得る、半導体部品の製造方法。
電気炉を用いて表1のセリウム源を800℃、空気下で1時間焼成することによりセリウム酸化物粒子(セリア粒子)を得た。
上述のセリウム酸化物粒子の陽電子寿命の平均値を下記の手順で測定した。測定結果を表1に示す。
測定装置:東洋精鋼株式会社製、商品名「PSA Type L-II」
陽電子線源:薄膜陽電子線源(公益社団法人日本アイソトープ協会製)
総カウント数:1000000カウント
上述のセリウム酸化物粒子と、リン酸二水素アンモニウムと、水とを混合することにより懸濁液を得た。セリウム酸化物粒子の含有量は、懸濁液の全質量を基準として5質量%であり、リン酸二水素アンモニウムの含有量は、セリウム酸化物粒子100質量部に対して2質量部であった。
ブランケットウエハ(BKW)を次の手順で作製した。まず、表面に酸化ケイ素膜(SiO2、初期膜厚:2000nm)を有するφ200mmのパターンなしのウエハを準備した。次に、このウエハを20mm×20mmに切り抜くことにより研磨用のブランケットウエハを得た。
Claims (13)
- 砥粒を得るための原料の選定方法であって、
前記原料がセリウムを含み、
陽電子消滅法により測定される陽電子寿命の平均値に基づき前記原料を選定する、原料の選定方法。 - 前記原料がセリウム酸化物を含む、請求項1に記載の原料の選定方法。
- 砥粒を得るための原料であって、
セリウムを含み、
陽電子消滅法により測定される陽電子寿命の平均値が285~360psである、原料。 - セリウム酸化物を含む、請求項3に記載の原料。
- オキシ炭酸セリウム由来のセリウム酸化物を含む、請求項3に記載の原料。
- 炭酸セリウム由来のセリウム酸化物を含む、請求項3に記載の原料。
- トリメシン酸のセリウム錯体由来のセリウム酸化物を含む、請求項3に記載の原料。
- 請求項1又は2に記載の原料の選定方法により選定された原料、又は、請求項3~7のいずれか一項に記載の原料を粉砕する、砥粒の製造方法。
- 請求項8に記載の砥粒の製造方法により得られた砥粒と、水と、を混合する、研磨液の製造方法。
- 請求項9に記載の研磨液の製造方法により得られた研磨液を用いて被研磨部材を研磨する、研磨方法。
- 前記被研磨部材が酸化ケイ素を含む、請求項10に記載の研磨方法。
- 請求項10に記載の研磨方法により研磨された被研磨部材を用いて部品を得る、部品の製造方法。
- 請求項10に記載の研磨方法により研磨された被研磨部材を用いて半導体部品を得る、半導体部品の製造方法。
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| CN202380036913.6A CN119110837A (zh) | 2022-10-27 | 2023-05-09 | 用于获得磨粒的原料及其选择方法、磨粒的制造方法、研磨液的制造方法、研磨方法、零件的制造方法、以及半导体零件的制造方法 |
| US18/857,697 US20250263594A1 (en) | 2022-10-27 | 2023-05-09 | Raw material for obtaining abrasive grains and method for selecting same, abrasive grain production method, polishing solution production method, polishing method, component production method, and semiconductor component production |
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| JP2009113993A (ja) * | 2006-03-03 | 2009-05-28 | Hitachi Chem Co Ltd | 金属酸化物粒子、これを含む研磨材、この研磨材を用いた基板の研磨方法及び研磨して得られる半導体装置の製造方法 |
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| JP2010106994A (ja) | 2008-10-31 | 2010-05-13 | Ntn Corp | 流体軸受装置 |
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| SG11201906571TA (en) * | 2017-01-16 | 2019-08-27 | Jgc Catalysts & Chemicals Ltd | Polishing composition |
| US20210189176A1 (en) * | 2017-09-29 | 2021-06-24 | Hitachi Chemical Company, Ltd. | Polishing solution, polishing solution set, and polishing method |
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- 2023-05-09 KR KR1020257011482A patent/KR20250093486A/ko active Pending
- 2023-05-09 US US18/856,368 patent/US20250257252A1/en active Pending
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- 2023-05-09 WO PCT/JP2023/017468 patent/WO2024089922A1/ja not_active Ceased
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- 2023-05-09 CN CN202380037318.4A patent/CN119110790A/zh active Pending
- 2023-05-09 WO PCT/JP2023/017463 patent/WO2024089919A1/ja not_active Ceased
- 2023-05-09 WO PCT/JP2023/017465 patent/WO2024089921A1/ja not_active Ceased
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- 2023-05-09 JP JP2024552819A patent/JPWO2024089920A1/ja active Pending
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| JP2007129248A (ja) * | 1997-12-18 | 2007-05-24 | Hitachi Chem Co Ltd | 研磨剤及びスラリー |
| WO2000073211A1 (en) * | 1999-05-28 | 2000-12-07 | Hitachi Chemical Co., Ltd. | Method for producing cerium oxide, cerium oxide abrasive, method for polishing substrate using the same and method for manufacturing semiconductor device |
| KR20140087668A (ko) * | 2012-12-31 | 2014-07-09 | 주식회사 케이씨텍 | 세륨계 연마입자와 이를 포함하는 슬러리 및 그 제조 방법 |
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| WO2022070923A1 (ja) * | 2020-09-30 | 2022-04-07 | 昭和電工マテリアルズ株式会社 | スラリ、研磨方法及び半導体部品の製造方法 |
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| JPWO2024089922A1 (ja) | 2024-05-02 |
| WO2024089920A1 (ja) | 2024-05-02 |
| CN119110838A (zh) | 2024-12-10 |
| US20250257252A1 (en) | 2025-08-14 |
| US20250257253A1 (en) | 2025-08-14 |
| CN119110837A (zh) | 2024-12-10 |
| JPWO2024089919A1 (ja) | 2024-05-02 |
| JPWO2024089921A1 (ja) | 2024-05-02 |
| WO2024089921A1 (ja) | 2024-05-02 |
| WO2024089923A1 (ja) | 2024-05-02 |
| KR20250097807A (ko) | 2025-06-30 |
| KR20250096700A (ko) | 2025-06-27 |
| KR20250093485A (ko) | 2025-06-24 |
| JPWO2024089920A1 (ja) | 2024-05-02 |
| CN119110790A (zh) | 2024-12-10 |
| KR20250093486A (ko) | 2025-06-24 |
| US20250263593A1 (en) | 2025-08-21 |
| US20250263594A1 (en) | 2025-08-21 |
| CN119095932A (zh) | 2024-12-06 |
| WO2024089922A1 (ja) | 2024-05-02 |
| KR20250093484A (ko) | 2025-06-24 |
| CN119110791A (zh) | 2024-12-10 |
| JPWO2024089923A1 (ja) | 2024-05-02 |
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