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
• • 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
  • H10P52/40—Chemomechanical polishing [CMP]
  • H10P52/403—Chemomechanical polishing [CMP] of conductive or resistive materials
• • 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
  • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
  • B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
  • B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
• • 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
  • B24B53/00—Devices or means for dressing or conditioning abrasive surfaces
  • B24B53/017—Devices or means for dressing, cleaning or otherwise conditioning lapping tools
• • 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
  • C09K3/1436—Composite particles, e.g. coated particles
• • 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
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F71/00—Manufacture or treatment of devices covered by this subclass
  • H10F71/138—Manufacture of transparent electrodes, e.g. transparent conductive oxides [TCO] or indium tin oxide [ITO] electrodes

Definitions

• the present disclosure relates to a polishing agent, a polishing method, etc. used for polishing indium tin oxide (hereinafter referred to as "ITO").
• ITO indium tin oxide
• CMP Chemical mechanical polishing
• ITO has high light transmittance, conductivity, and durability, it is used in flat panel displays and the like. Furthermore, in recent years, ITO has attracted attention as a protective material for semiconductor optical devices (see, for example, Patent Documents 1 and 2 below). CMP can be used to polish ITO, and abrasives used to polish ITO are known (for example, see Patent Document 3 below)
• the polishing agent used for polishing ITO is required to further improve the polishing rate for ITO (ITO polishing rate).
• One aspect of the present disclosure aims to provide a polishing agent capable of obtaining an excellent ITO polishing rate.
• Another aspect of the present disclosure aims to provide a polishing method using the polishing agent.
• abrasive grains containing silica and having a positive zeta potential, and dicarboxylic acids having 3 or less carbon atoms and salts thereof can be used as polishing agents with a pH of 9.0 or less. It has been found that an excellent ITO polishing rate can be obtained by using at least one dicarboxylic acid component selected from the group consisting of:
• a polishing agent for polishing a polished surface containing ITO which comprises abrasive grains, at least one dicarboxylic acid component selected from the group consisting of dicarboxylic acids having 3 or less carbon atoms and salts thereof, and water. and the abrasive grains contain silica, have a positive zeta potential, and have a pH of 9.0 or less.
• the polishing agent according to [1], wherein the abrasive grains contain colloidal silica.
• the constituent components of the abrasive according to any one of [1] to [13] are divided into a first liquid and a second liquid, and the first liquid contains the abrasive grains and water. , wherein the second liquid contains the dicarboxylic acid component and water.
• a polishing method comprising the step of polishing a surface to be polished containing ITO using the polishing agent according to any one of [1] to [13].
• polishing agent that can obtain an excellent ITO polishing rate.
• a polishing method using the polishing agent 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.
• (Meth)acrylic means at least one of acrylic and methacrylic corresponding thereto. The same applies to other similar expressions such as "(meth)acryloyl”.
• “Polishing rate” means the rate at which the material to be polished is removed by polishing (for example, the amount of reduction in the thickness of the material to be polished per hour; Removal Rate).
• the term "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 according to this embodiment is an abrasive for polishing a surface to be polished containing ITO.
• the abrasive according to the present embodiment includes abrasive grains, at least one dicarboxylic acid component (hereinafter referred to as "dicarboxylic acid component A") selected from the group consisting of dicarboxylic acids having 3 or less carbon atoms and salts thereof, and water. Contains.
• the abrasive grains contain silica and have a positive zeta potential.
• the pH of the polishing agent according to this embodiment is 9.0 or less.
• the polishing agent according to the present embodiment it is possible to obtain an excellent ITO polishing rate, and in the evaluation of Examples described later, it is possible to obtain an ITO polishing rate of 50 nm/min or more (preferably 100 nm/min or more). I can do it.
• the present inventors speculate as follows about the reason why such a polishing rate is obtained. However, the reasons are not limited to the following. That is, by coordinating dicarboxylic acid component A to ITO in a polishing agent having a pH of 9.0 or less, a state in which ITO is easily polished is obtained.
• silica In abrasive grains that contain silica and have a positive zeta potential, silica has a higher affinity for ITO than abrasive grains that have a negative zeta potential, so the frequency of contact between the abrasive grains containing silica and ITO is higher. increases. It is presumed that these effects result in an excellent ITO polishing rate.
• the polishing agent according to this embodiment at least a portion of the ITO can be removed by polishing the surface to be polished that includes ITO. According to this embodiment, it is possible to provide the use of an abrasive for polishing ITO.
• the polishing agent according to this embodiment can be used as a CMP polishing agent.
• the polishing agent according to this embodiment contains abrasive grains containing silica.
• abrasive grains containing silica silica particles (particles containing silica) such as colloidal silica and fumed silica can be used.
• the abrasive grains may contain colloidal silica from the viewpoints of easily obtaining an excellent ITO polishing rate, easily suppressing the occurrence of polishing scratches, and easily selecting the particle size.
• Abrasive grains have a positive zeta potential (positive charge) in the polishing agent.
• the zeta potential of the abrasive grains in the polishing agent is measured, and if the value exceeds 0 mV, it can be determined that the abrasive grains have a positive zeta potential.
• the zeta potential of the abrasive grains may be 10 mV or more, 15 mV or more, or 18 mV or more from the viewpoint of easily obtaining an excellent ITO polishing rate and from the viewpoint of easily obtaining good storage stability.
• the upper limit of the zeta potential is not particularly limited, but is, for example, 100 mV or less.
• the zeta potential can be measured using, for example, DELSA NANO C manufactured by Beckman Coulter.
• Zeta potential ( ⁇ [mV]) is defined as the scattering intensity of a measurement sample in a zeta potential measuring device of 1.0 ⁇ 10 4 to 5.0 ⁇ 10 4 cps (“cps” is counts per second (i.e., counts per second).
• cps counts per second (i.e., counts per second).
• the abrasive After diluting the abrasive with pure water to obtain a measurement sample such that the abrasive has a particle count of 0.0000000000000000000000000000000000,000,000,000 0000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000
• Methods for adjusting the abrasive grains so that they have a positive zeta potential in the abrasive include methods that control the manufacturing method of the abrasive grains, methods that adjust the pH of the abrasive grains, and methods that perform surface treatment on the abrasive grains. Can be mentioned. Although silica particles generally have a negative zeta potential (negative charge) in a liquid, they tend to have a positive zeta potential by lowering the pH. Furthermore, as a method for surface-treating abrasive grains, silica particles can also be surface-treated using a coupling agent having a cationic group.
• the abrasive grains can contain constituent materials other than silica.
• constituent materials include alumina, ceria, zirconia, and cerium hydroxide.
• the silica content in the abrasive grains is determined based on the total mass of the abrasive grains (the entire abrasive grains included in the abrasive), from the viewpoint of easily obtaining an excellent ITO polishing speed and from the viewpoint of easily suppressing the occurrence of polishing scratches. , 50% by mass or more, more than 50% by mass, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 99% by mass or more good.
• the abrasive grains may be made of silica (substantially 100% by mass of the abrasive grains contained in the abrasive is silica).
• the average particle size (average secondary particle size) of the abrasive grains is 10 nm or more, 20 nm or more, 30 nm or more, 40 nm or more, from the viewpoint that it is easy to obtain sufficient mechanical polishing force and therefore easy to obtain an excellent ITO polishing rate. It may be 50 nm or more, more than 50 nm, or 60 nm or more.
• the average particle diameter of the abrasive grains is 200 nm or less, 180 nm or less, 150 nm or less, 120 nm or less, 100 nm or less, 80 nm or less, 70 nm or less, or 60 nm or less, from the viewpoint of easily obtaining good dispersion stability of the abrasive grains. It's fine. From these viewpoints, the average particle size of the abrasive grains may be 10 to 200 nm, 20 to 100 nm, or 30 to 80 nm.
• the average particle size of abrasive grains can be measured by photon correlation method.
• the average particle diameter can be measured using a device such as Delsa MAX Pro manufactured by Beckman Coulter.
• the measurement method using Delsa MAX Pro is as follows. For example, prepare an aqueous dispersion with an abrasive grain content of 2.0% by mass, put about 4 mL of this aqueous dispersion into a 1 cm square cell (L indicates "liter"; the same applies hereinafter), and then place it inside the device. Set up a cell in . The value obtained by setting the refractive index of the dispersion medium to 1.33 and the viscosity to 0.887 mPa ⁇ s and performing measurement at 25° C. can be adopted as the average particle diameter of the abrasive grains.
• the content of abrasive grains may be in the following range based on the total mass of the abrasive.
• the content of abrasive grains is 0.1% by mass or more, 0.5% by mass or more, 1.0% by mass or more, from the viewpoint that it is easy to obtain sufficient mechanical polishing force and thus an excellent ITO polishing rate. , more than 1.0 mass%, 1.5 mass% or more, 2.0 mass% or more, more than 2.0 mass%, 2.5 mass% or more, 3.0 mass% or more, 3.5 mass% or more, It may be 4.0% by mass or more, 4.5% by mass or more, or 5.0% by mass or more.
• the content of abrasive grains was determined to be 20 mass by weight, from the viewpoint of easily avoiding increase in viscosity of the abrasive, easy to avoid agglomeration of abrasive grains, easy to suppress the occurrence of polishing scratches, easy to handle the abrasive, etc. % or less, 15% by mass or less, 10% by mass or less, 8.0% by mass or less, 6.0% by mass or less, 5.0% by mass or less, less than 5.0% by mass, 4.5% by mass or less, 4. It may be 0% by mass or less, 3.5% by mass or less, 3.0% by mass or less, 2.5% by mass or less, or 2.0% by mass or less. From these viewpoints, the content of abrasive grains may be 0.1 to 20% by mass, 0.5 to 10% by mass, 1 to 6% by mass, or 1 to 5% by mass.
• the polishing slurry according to the present embodiment contains at least one dicarboxylic acid component A selected from the group consisting of dicarboxylic acids having 3 or less carbon atoms and salts thereof as an acid component. . It is assumed that dicarboxylic acids having 4 or more carbon atoms and their salts are sterically hindered and difficult to coordinate with ITO. Carboxylic acids and their salts that do not fall under dicarboxylic acids do not have a chelating effect, so it is presumed that they are difficult to coordinate with ITO.
• dicarboxylic acid component A examples include oxalic acid, malonic acid, and salts thereof.
• the salt include alkali metal salts (eg, sodium salts).
• the dicarboxylic acid component A may contain at least one selected from the group consisting of oxalic acid, malonic acid, and salts thereof, from the viewpoint of easily obtaining an excellent ITO polishing rate.
• Dicarboxylic acid component A may contain at least one selected from the group consisting of oxalic acid and its salts, and may contain at least one selected from the group consisting of malonic acid and its salts.
• the polishing slurry according to this embodiment may contain an acid component other than the dicarboxylic acid component A.
• acid components include organic acid components and inorganic acid components.
• Organic acid components 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, succinic acid, adipic acid, glutaric acid, malic acid, citric acid, pimelic acid, maleic acid Acid, phthalic acid, pyruvic acid, lactic acid, glycine, asparagine, ⁇ -alanine, ⁇ -alanine, glutamic acid, glutamine, valine, leucine, isoleucine, lysine, serine, threonine, phenylalanine, tyrosine, methionine, tryptophan, salts thereof ( Examples include alkali metal salts such as sodium salts.
• the inorganic acid component include nitric acid, sulfuric acid, phosphoric acid, and the like.
• the acid component may be used as a pH adjuster to adjust the pH of the polishing agent.
• the content of dicarboxylic acid component A in the acid component is 50% by mass or more, 50% by mass based on the total mass of the acid component (all the acid components contained in the polishing agent) from the viewpoint of easily obtaining an excellent ITO polishing rate. It may be more than 60% by mass, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 99% by mass or more.
• the acid component may be composed of dicarboxylic acid component A (substantially 100% by mass of the acid component contained in the polishing agent is dicarboxylic acid component A).
• the content of the acid component (the total amount of compounds corresponding to the acid component) or the content of the dicarboxylic acid component A should be within the following range based on the total mass of the polishing agent, from the viewpoint of easily obtaining an excellent ITO polishing rate. It's fine.
• the content of the acid component or the content of the dicarboxylic acid component A is 0.001% by mass or more, 0.005% by mass or more, 0.01% by mass or more, 0.02% by mass or more, 0.03% by mass or more, It may be 0.04% by mass or more, 0.05% by mass or more, 0.08% by mass or more, 0.10% by mass or more, 0.12% by mass or more, or 0.14% by mass or more.
• the content of the acid component or the content of the dicarboxylic acid component A is 5.0% by mass or less, 4.0% by mass or less, 3.0% by mass or less, 2.0% by mass or less, 1.0% by mass or less, 0.80 mass% or less, 0.50 mass% or less, 0.40 mass% or less, 0.30 mass% or less, 0.20 mass% or less, 0.15 mass% or less, 0.14 mass% or less, 0 It may be .12% by mass or less, or 0.10% by mass or less.
• the content of the acid component or the content of the dicarboxylic acid component A is 0.001 to 5.0% by mass, 0.005 to 1.0% by mass, 0.01 to 0.30% by mass, Alternatively, it may be 0.01 to 0.20% by mass.
• the content of the acid component or the dicarboxylic acid component A may be in the following range with respect to 100 parts by mass of the abrasive grains.
• the content of the acid component or dicarboxylic acid component A is 0.1 parts by mass or more, 0.5 parts by mass or more, 1.0 parts by mass or more, 1.2 parts by mass from the viewpoint of easily obtaining an excellent ITO polishing rate.
• the amount may be 1.5 parts by mass or more, 1.8 parts by mass or more, 2.0 parts by mass or more, 2.3 parts by mass or more, 2.5 parts by mass or more, or 2.8 parts by mass or more.
• the content of the acid component or the dicarboxylic acid component A is 10 parts by mass or less, 8.0 parts by mass or less, 6.0 parts by mass or less, 5.0 parts by mass or less, from the viewpoint of easily obtaining an excellent ITO polishing rate.
• the amount may be 4.0 parts by mass or less, 3.0 parts by mass or less, or 2.8 parts by mass or less.
• the content of the acid component or the dicarboxylic acid component A may be 2.5 parts by mass or less, 2.3 parts by mass or less, or 2.0 parts by mass or less. From these viewpoints, the content of the acid component or the dicarboxylic acid component A may be 0.1 to 10 parts by mass, 0.5 to 5.0 parts by mass, or 1.0 to 3.0 parts by mass. .
• the polishing slurry according to the present embodiment may contain a cationic surfactant (excluding compounds corresponding to acid components) from the viewpoint of easily obtaining an excellent ITO polishing rate.
• cationic surfactant examples include onium salts such as ammonium salts and phosphonium salts.
• Cationic surfactants may include onium salts (such as ammonium salts) having carbon-carbon unsaturated bonds (such as carbon-carbon unsaturated double bonds). The number of carbon-carbon unsaturated bonds in an onium salt (ammonium salt, etc.) having carbon-carbon unsaturated bonds may be one or two.
• Examples of counter anions of onium salts include halide ions (chloride ions, bromide ions, etc.), sulfate ions, alkyl sulfate ions, nitrate ions, and the like.
• the counter anion may be at least one type selected from the group consisting of halide ions and alkyl sulfate ions, and may be a halide ion, from the viewpoint of easily obtaining an excellent ITO polishing rate.
• the halide ion may be at least one type selected from the group consisting of chloride ions and bromide ions, and may be chloride ions, from the viewpoint of easily obtaining an excellent ITO polishing rate.
• the cationic surfactant may include an onium salt having one counter anion or an ammonium salt having one counter anion from the viewpoint of easily obtaining an excellent ITO polishing rate.
• the cationic surfactant may contain an ammonium salt, from the viewpoint of easily obtaining an excellent ITO polishing rate, and an ammonium salt having one or two nitrogen atoms (a compound having one or two nitrogen atoms). and may include ammonium salts with one quaternary nitrogen atom (compounds with one quaternary nitrogen atom).
• the ammonium salt may have an alkyl group, an unsaturated hydrocarbon group (such as an allyl group), an aromatic group (such as a phenyl group), etc. as a functional group bonded to a nitrogen atom.
• the ammonium salt may include an alkyl ammonium salt from the viewpoint of easily obtaining an excellent ITO polishing rate.
• the alkyl group of the alkylammonium salt may be unsubstituted or substituted.
• substituents for the alkyl group include a hydroxy group, an alkoxy group, a carboxy group, a carboxylic acid group, an amide group, a (meth)acrylamide group, and a (meth)acryloyloxy group.
• the ammonium salt may include an alkyl ammonium salt having an alkyl group substituted with a (meth)acrylamide group from the viewpoint of easily obtaining an excellent ITO polishing rate.
• the number of unsubstituted alkyl groups (alkyl groups bonded to the nitrogen atom) or the number of unsubstituted methyl groups (methyl groups bonded to the nitrogen atom) can be adjusted to obtain an excellent ITO polishing rate. From a simple standpoint, it may be 1 to 4, 2 to 4, 3 to 4, or 2 to 3.
• alkylammonium salt examples include tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, (3-acrylamidopropyl)trimethylammonium salt, and 2-((meth)acryloyloxy)ethyltrimethylammonium salt (for example, methacroylcholine salt).
• alkylammonium salts such as; trialkylammonium salts; dialkylammonium salts; diallyldialkylammonium salts such as diallyldimethylammonium salt; monoalkylammonium salts.
• the cationic surfactant may include at least one selected from the group consisting of tetraalkylammonium salts and diallyldialkylammonium salts from the viewpoint of easily obtaining an excellent ITO polishing rate.
• Examples of the phosphonium salt include tetramethylphosphonium salt, tetraethylphosphonium salt, tetraphenylphosphonium salt, and the like.
• the cationic surfactant may contain a compound (ammonium salt, etc.) having the following molecular weight from the viewpoint of easily obtaining an excellent ITO polishing rate.
• the molecular weight may be 500 or less, 450 or less, 400 or less, 350 or less, 300 or less, 250 or less, 220 or less, 200 or less, 180 or less, 150 or less, or 120 or less.
• the molecular weight may be 50 or more, 80 or more, 100 or more, 120 or more, 150 or more, 180 or more, or 200 or more. From these points of view, the molecular weight may be from 50 to 500, from 80 to 400, or from 100 to 250.
• the content of ammonium salt in the cationic surfactant is 50% based on the total mass of the cationic surfactant (the entire cationic surfactant contained in the polishing agent) from the viewpoint of easily obtaining an excellent ITO polishing rate. It may be at least 50% by mass, at least 60% by mass, at least 70% by mass, at least 80% by mass, at least 90% by mass, at least 95% by mass, at least 98% by mass, or at least 99% by mass.
• the cationic surfactant may be made of an ammonium salt (substantially 100% by mass of the cationic surfactant contained in the polishing agent is ammonium salt).
• the content of the cationic surfactant may be in the following range based on the total mass of the polishing agent. From the viewpoint of easily obtaining an excellent ITO polishing rate, the content of the cationic surfactant is 0.005% by mass or more, 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, It may be 0.06% by mass or more, 0.08% by mass or more, or 0.10% by mass or more.
• the content of the cationic surfactant is 5.0% by mass or less, 3.0% by mass or less, 1.0% by mass or less, from the viewpoint of easily obtaining an excellent ITO polishing rate and easily preventing agglomeration of abrasive grains.
• the content of the cationic surfactant may be 0.08% by mass or less or 0.06% by mass or less from the viewpoint of adjusting the ITO polishing rate. From these viewpoints, the content of the cationic surfactant may be 0.005 to 5.0% by mass, 0.01 to 1.0% by mass, or 0.05 to 0.50% by mass. .
• the content of the cationic surfactant may be 0.01% by mass or less, 0.001% by mass or less, or 0.0001% by mass or less, and may be substantially 0% by mass (this embodiment (The abrasive according to this embodiment does not need to contain a cationic surfactant).
• the content of the cationic surfactant may be in the following range based on 100 parts by mass of the abrasive grains. From the viewpoint of easily obtaining an excellent ITO polishing rate, the content of the cationic surfactant is 0.1 parts by mass or more, 0.5 parts by mass or more, 1.0 parts by mass or more, 1.2 parts by mass or more, The amount may be 1.5 parts by mass or more, 1.8 parts by mass or more, or 2.0 parts by mass or more. From the viewpoint of adjusting the ITO polishing rate, the content of the cationic surfactant is 2.3 parts by mass or more, 2.5 parts by mass or more, 2.8 parts by mass or more, or 3.0 parts by mass or more. It's fine.
• the content of the cationic surfactant is 10 parts by mass or less, 8.0 parts by mass or less, and 6.0 parts by mass from the viewpoint of easily obtaining an excellent ITO polishing rate and easily preventing agglomeration of abrasive grains. 5.0 parts by mass or less, 4.0 parts by mass or less, 3.0 parts by mass or less, 2.8 parts by mass or less, 2.5 parts by mass or less, 2.3 parts by mass or less, or 2.0 parts by mass or less It may be less than 100 yen.
• the content of the cationic surfactant may be 1.8 parts by mass or less, 1.5 parts by mass, or 1.2 parts by mass from the viewpoint of adjusting the ITO polishing rate.
• the content of the cationic surfactant may be 0.1 to 10 parts by weight, 0.5 to 5.0 parts by weight, or 1.0 to 3.0 parts by weight.
• the content of the cationic surfactant may be 0.01 parts by mass or less, 0.001 parts by mass or less, or 0.0001 parts by mass or less, and may be substantially 0 parts by mass.
• the content of the cationic surfactant may be in the following range based on 100 parts by mass of the acid component or dicarboxylic acid component A.
• the content of the cationic surfactant is 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass from the viewpoint of easily obtaining an excellent ITO polishing rate.
• the amount may be 50 parts by mass or more, 60 parts by mass or more, or 70 parts by mass or more.
• the content of the cationic surfactant may be 80 parts by mass or more, 100 parts by mass or more, 120 parts by mass or more, or 150 parts by mass or more.
• the content of the cationic surfactant is 500 parts by mass or less, 400 parts by mass or less, 300 parts by mass or less, 250 parts by mass or less, 200 parts by mass or less, 150 parts by mass from the viewpoint of easily obtaining an excellent ITO polishing rate.
• the amount may be 120 parts by mass or less, 100 parts by mass or less, or 80 parts by mass or less.
• the content of the cationic surfactant may be 70 parts by mass or less or 60 parts by mass or less from the viewpoint of adjusting the ITO polishing rate. From these viewpoints, the content of the cationic surfactant may be 1 to 500 parts by weight, 10 to 300 parts by weight, or 50 to 200 parts by weight.
• the content of the cationic surfactant may be 0.1 parts by mass or less, 0.01 parts by mass or less, or 0.001 parts by mass or less, and may be substantially 0 parts by mass.
• the polishing agent according to this embodiment contains water.
• Water can be used as a dispersion medium or solvent for other components. Impurities in the water may be reduced to prevent interfering with the effects of other ingredients. Examples of water include pure water and ultrapure water obtained by removing impurity ions with an ion exchange resin and then passing through a filter to remove foreign substances; distilled water, and the like.
• the polishing agent according to the present embodiment may contain other additives as components other than the abrasive grains, acid component, cationic surfactant, and water. Such additives may be used for purposes such as improving the dispersibility of abrasive grains in the polishing agent, improving the chemical stability of the polishing agent, and increasing the polishing rate. Examples of additives include base components, organic solvents, corrosion inhibitors, antifoaming agents, and the like. The content of additives in the polishing agent can be arbitrarily determined.
• Examples of the base component include ammonia, sodium hydroxide, potassium hydroxide, TMAH (tetramethylammonium hydroxide), and the like.
• organic solvents examples include carbonate esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; lactones such as butyrolactone and propiolactone; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and triethylene.
• Glycol tripropylene glycol, methanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, butanetriol, pentanetriol, hexanetriol, heptanetriol, octanetriol, nonanetriol Glycols such as , decanetriol, erythritol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol Monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl mono
• glycol monoethers ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl Ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, diethylene glycol dipropyl ether, dipropylene glycol dipropyl ether, triethylene glycol dipropyl ether, tripropylene glycol dipropyl Examples include derivatives of glycols such as glycol diethers such as ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol dibutyl
• metal corrosion inhibitors examples include triazole compounds (compounds having a triazole skeleton), pyridine compounds, pyrazole compounds, pyrimidine compounds, imidazole compounds, guanidine compounds, thiazole compounds, tetrazole compounds, triazine compounds, hexamethylenetetramine, and the like.
• the pH of the polishing agent according to this embodiment is 9.0 or less from the viewpoint of obtaining an excellent ITO polishing rate.
• the pH of the abrasive is 8.0 or less, 7.0 or less, less than 7.0, from the viewpoint of easily obtaining an excellent ITO polishing rate, and from the viewpoint of easily obtaining good dispersion stability of the abrasive grains. It may be 6.0 or less, 5.0 or less, 4.0 or less, 3.5 or less, 3.3 or less, or 3.2 or less. From the viewpoint of adjusting the ITO polishing rate, the pH of the polishing agent may be 3.1 or less, 3.0 or less, less than 3.0, 2.9 or less, 2.8 or less, or 2.6 or less. .
• the pH of the polishing agent is 1.0 or more, 1.5 or more, 2.0 or more, more than 2.0, or 2. It may be .5 or more, 2.6 or more, 2.8 or more, 2.9 or more, 3.0 or more, more than 3.0, 3.1 or more, or 3.2 or more. From these viewpoints, the pH of the polishing agent is 1.0 to 9.0, 2.0 to 7.0, 2.5 to 5.0, 2.9 to 5.0, 3.0 to 4.0. , or more than 3.0 and less than or equal to 4.0.
• the pH of the polishing agent may be adjusted, for example, with the above-mentioned acid component, base component, and the like.
• the pH of the polishing agent is defined as the pH at a liquid temperature of 25°C.
• the pH of the abrasive can be measured with a pH meter using a general glass electrode (for example, Model (F-51) manufactured by Horiba, Ltd.).
• the pH of the polishing agent can be determined using, for example, a phthalate pH standard solution (pH 4.01), a neutral phosphate pH standard solution (pH 6.86), and a borate pH standard solution (pH 9.18) as pH standard solutions.
• a phthalate pH standard solution pH 4.01
• a neutral phosphate pH standard solution pH 6.86
• a borate pH standard solution pH 9.18
• the abrasive according to the present embodiment may be stored as a one-component abrasive containing abrasive grains, dicarboxylic acid component A, and water, and can be used as an abrasive to obtain a one-component abrasive by diluting with water. It may be stored as a stock solution, or it may be stored as a multi-part polishing agent in which the components of the one-component polishing agent are separated into a plurality of liquids.
• a one-component abrasive can be obtained by diluting the abrasive stock solution with water before or during use.
• Abrasive storage liquids differ from one-component abrasives in that they contain less water than one-component abrasives.
• the dilution ratio may be, for example, 1.5 times or more (when obtaining a one-component abrasive by adding water to the abrasive storage solution, the mass of the one-component abrasive is equal to the mass of the abrasive storage solution). (The dilution may be 1.5 times that of
• the liquid stability of the polishing agent can be improved, and the cost and space required for transportation, storage, etc. of the polishing agent can be reduced.
• the constituent components of the one-component polishing agent are mixed into the first liquid and the second liquid so that the first liquid and the second liquid are mixed to form a one-component polishing agent. It's okay to be divided.
• the multi-liquid polishing agent includes, for example, a first liquid containing abrasive grains and water, and a second liquid containing dicarboxylic acid component A and water.
• Components other than the abrasive grains, dicarboxylic acid component A, and water can be included in the first liquid, second liquid, or other liquid as appropriate; for example, they can be included in the second liquid.
• the first liquid and the second liquid in the multi-component abrasive may be mixed just before polishing or during polishing to prepare the abrasive, and the first liquid and the second liquid in the multi-component abrasive are mixed, respectively.
• the abrasive may be prepared by supplying the first liquid and the second liquid onto a polishing plate and mixing the first liquid and the second liquid on the polishing plate.
• the constituent components of the one-part polishing slurry may be stored separately into three or more parts.
• the polishing method according to the present embodiment includes a polishing step (for example, a CMP step) of polishing a surface to be polished containing ITO (indium tin oxide) using the abrasive according to the present embodiment.
• a polishing step for example, a CMP step
• ITO indium tin oxide
• the abrasive used in the polishing process may be a one-component abrasive, an abrasive obtained by diluting an abrasive storage liquid with water, or a multi-component abrasive in which multiple liquids (i.e.
• the polishing agent may be obtained by mixing the first liquid, the second liquid, etc.).
• a substrate having a surface to be polished containing ITO can be polished.
• the base body may include, for example, an ITO member (a member containing ITO) having recesses and protrusions on its surface, and other members (for example, a member containing an insulating material, a metal material, etc.).
• the abrasive according to the present embodiment is used to polish the ITO member of the base having the ITO member and the insulating member (member containing the insulating material), and the polishing may be stopped when the insulating member is exposed. .
• the surface to be polished of the substrate is pressed against the polishing cloth (polishing pad) of the polishing table, an abrasive is supplied between the surface to be polished and the polishing cloth, and the back surface of the substrate (the surface to be polished and The surface to be polished can be polished by moving the base body relative to the polishing surface plate while applying a predetermined pressure to the opposite surface (opposite surface).
• a general polishing device which has a polishing surface plate to which a polishing cloth can be attached, which is equipped with a motor that can change the number of revolutions, and a holder that holds the substrate.
• the polishing cloth is not particularly limited, but common nonwoven fabrics, foamed polyurethane, porous fluororesin, etc. can be used.
• polishing agent may be continuously supplied to the polishing cloth using a pump or the like.
• the amount of abrasive to be supplied the surface of the polishing cloth may always be covered with the abrasive, and products generated as the polishing progresses may be continuously discharged.
• the polishing method according to this embodiment may include a step of preparing a substrate to be polished before the polishing step.
• the polishing method according to the present embodiment may include an abrasive preparation step of diluting the abrasive storage solution with water to obtain an abrasive before the polishing step.
• the polishing method according to the present embodiment mixes a plurality of liquids (first liquid, second liquid, etc.) in the multi-component abrasive before the polishing process, and performs polishing.
• the method may include a step of preparing an abrasive to obtain an abrasive.
• the polishing method according to the present embodiment may include a polishing cloth conditioning step before the polishing step, from the viewpoint of performing polishing while keeping the surface state of the polishing cloth always the same.
• the polishing cloth can be conditioned with a liquid containing at least water using, for example, a dresser equipped with diamond particles.
• the polishing method according to this embodiment may include a substrate cleaning step after the polishing step.
• the substrate may be thoroughly washed under running water and then dried using a spin dryer or the like to remove water droplets adhering to the substrate.
• the substrate may be cleaned using a known cleaning method (for example, a method in which deposits on the substrate are removed by flowing a commercially available cleaning solution onto the surface of the substrate and rotating a polyurethane brush while pressing the brush against the substrate with a constant pressure). It may be dried after washing.
• the component manufacturing method according to the present embodiment includes a singulation step of singulating the substrate 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 component manufacturing method according to the present embodiment may include a polishing step of polishing the substrate by the polishing method according to the present embodiment before the singulation step.
• the component according to this embodiment is, for example, a chip (for example, a semiconductor chip).
• the component according to the present embodiment is a component obtained by the component manufacturing method according to the present embodiment.
• the electronic device according to this embodiment includes the component according to this embodiment.
• Potassium oxide (KOH) aqueous solution was added.
• the amount of potassium hydroxide aqueous solution was adjusted so that the pH shown in Table 1 or Table 2 was obtained.
• the amount of ultrapure water (X parts by mass) was adjusted so that 100 parts by mass of the abrasive was obtained.
• the number of carbon atoms and the number of carboxy groups in each acid component are as follows. Oxalic acid: 2 carbon atoms, 2 carboxy groups Malonic acid: 3 carbon atoms, 2 carboxy groups Pyruvic acid: 3 carbon atoms, 1 carboxy group Lactic acid: 3 carbon atoms, 1 carboxy group Succinic acid: 4 carbon atoms, 2 carboxy groups Glutaric acid: 5 carbon atoms, 2 carboxy groups
• Ammonium salt A Diallyldimethylammonium chloride, manufactured by Tokyo Chemical Industry Co., Ltd.
• Ammonium salt B Tetramethylammonium bromide, manufactured by Tokyo Chemical Industry Co., Ltd.
• Ammonium salt C Methacroylcholine chloride (also known as 2-(methacryloyloxy)ethyltrimethylammonium chloride) ), manufactured by Tokyo Chemical Industry Co., Ltd.
• Ammonium salt D (3-acrylamidopropyl) trimethylammonium chloride, manufactured by Tokyo Chemical Industry Co., Ltd.
• Ammonium salt E 2-(methacryloyloxy)ethyltrimethylammonium methyl sulfate, Fuji Film Wako Chemical Co., Ltd. Company made
• the average particle size of the abrasive grains was measured using Delsa MAX Pro manufactured by Beckman Coulter. First, an aqueous dispersion having an abrasive grain content of 2.0% by mass was prepared using the above-mentioned abrasive. After putting about 4 mL of this aqueous dispersion into a 1 cm square cell, the cell was installed in the apparatus. The average particle size of the abrasive grains was measured by setting the refractive index of the dispersion medium to 1.33 and the viscosity to 0.887 mPa ⁇ s, and performing the measurement at 25°C. In all of the Examples and Comparative Examples, the average particle size (secondary particle size) of the abrasive grains was 60 nm.
• zeta potential of abrasive grains in the polishing slurry was measured using a zeta potential measuring device (trade name: DELSA NANO C, manufactured by Beckman Coulter).
• a sample was obtained by diluting the abrasive with pure water so that the scattering intensity of the measurement sample was 1.0 ⁇ 10 4 to 5.0 ⁇ 10 4 cps using a zeta potential measuring device. Thereafter, the sample was placed in a cell for measuring zeta potential, and the zeta potential was measured.
• the surface of the abrasive grains was positively charged in the polishing agent.
• a substrate obtained by cutting a laminate having a 200 nm thick ITO film on a silicon substrate into 2 cm square pieces was used as the substrate to be polished.
• the above-described substrate was fixed to a holder (a holder to which a suction pad for attaching the substrate was attached) of a polishing device (manufactured by NanoFactor Co., Ltd., FACT-200).
• a holder was placed on a polishing surface plate to which a foamed polyurethane polishing cloth was attached so that the ITO film faced the polishing cloth.
• a weight was placed so that the processing load was adjusted to 0.34 kgf/cm 2 .
• the ITO film was polished for 30 seconds at a plate rotation rate of 90 min -1 and a head rotation rate of 87 min -1 while dropping the above-mentioned abrasive onto the polishing plate at a rate of 15 mL/min.
• the ITO polishing rate was calculated from the difference in thickness obtained by measuring the thickness of the ITO film before and after polishing.
• a film thickness measuring device F40 manufactured by Filmetrics Co., Ltd. was used to measure the film thickness. The results are shown in Tables 1 and 2. In the examples, it was confirmed that an excellent ITO polishing rate could be obtained.

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• 2022
  • 2022-04-20 JP JP2024515813A patent/JPWO2023203680A1/ja active Pending
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