Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09G—POLISHING COMPOSITIONS; SKI WAXES
  • C09G1/00—Polishing compositions
  • C09G1/02—Polishing compositions containing abrasives or grinding agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B24—GRINDING; POLISHING
  • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
  • B24B37/00—Lapping machines or devices; Accessories
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/14—Anti-slip materials; Abrasives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/14—Anti-slip materials; Abrasives
  • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
• • 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
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
  • H10P52/40—Chemomechanical polishing [CMP]
  • H10P52/402—Chemomechanical polishing [CMP] of semiconductor materials
• • 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
  • H10P90/00—Preparation of wafers not covered by a single main group of this subclass, e.g. wafer reinforcement
  • H10P90/12—Preparing bulk and homogeneous wafers
  • H10P90/129—Preparing bulk and homogeneous wafers by polishing

Definitions

• the present invention relates to a polishing composition, a concentrated solution of the polishing composition, and a polishing method.
• Japanese Patent No. 4668528 (corresponding to the specification of U.S. Patent Application Publication No. 2005/054203) discloses that a polishing composition containing abrasive grains, a block polyether of polyethylene oxide and polypropylene oxide, a basic compound, at least one selected from hydroxyethyl cellulose and polyvinyl alcohol, and water increases the polishing speed for silicon wafers and improves the surface quality after polishing.
• the present invention was made in consideration of these circumstances, and its purpose is to provide a means for improving the surface quality of the object to be polished after polishing.
• One aspect of the present invention is a polishing composition that includes an abrasive grain, a compound ⁇ having a specific structure, a water-soluble polymer different from compound ⁇ , a basic compound, and a dispersion medium.
• compound ⁇ is contained in a specific amount, and each component is blended so that the ratio of the total mass of compound ⁇ and the water-soluble polymer to the mass of the abrasive grain is within a specific range.
• Such a polishing composition can maintain the surface quality of the polished object after polishing in a good condition. Therefore, according to this aspect, a polishing composition that can improve the surface quality of the polished object after polishing is provided.
• the inventors speculate as follows about the mechanism by which such an effect is obtained by the polishing composition according to this aspect. However, the following mechanism is merely speculation, and the scope of the present invention is not limited thereby.
• the compound ⁇ has a polyethylene oxide structure and a polypropylene oxide structure, and thus adsorbs to the surface of the object to be polished during polishing, suppressing mechanical polishing and chemical polishing of the surface of the object to be polished.
• the water-soluble polymer can act as a buffer for the abrasive grains during polishing.
• the water-soluble polymer adsorbs to the surface of the object to be polished during polishing, suppresses mechanical polishing on the surface of the object to be polished, reduces the unevenness of the object to be polished, and has the effect of suppressing the adhesion of particles to the surface of the object to be polished after polishing.
• the polishing composition according to this embodiment contains the compound ⁇ and the water-soluble polymer having these effects at a specific mass ratio relative to the abrasive grains, thereby significantly improving the quality of the surface of the object to be polished.
• the polishing composition according to this embodiment can reduce defects on the surface of the object to be polished while maintaining a good polishing rate or improving the polishing rate.
• the polishing composition according to this embodiment contains abrasive grains.
• the abrasive grains have the effect of mechanically polishing the object to be polished, and improve the polishing rate of the object to be polished by the polishing composition.
• the abrasive grains contained in the polishing composition according to this embodiment are not particularly limited, and examples thereof include inorganic particles, organic particles, and organic-inorganic composite particles. Among these, inorganic particles are preferred.
• the abrasive grains contain inorganic particles.
• the inorganic particles are not particularly limited, and examples thereof include oxide particles such as silica particles, alumina particles, cerium oxide particles, chromium oxide particles, titanium dioxide particles, zirconium oxide particles, magnesium oxide particles, manganese dioxide particles, zinc oxide particles, and red iron oxide particles; nitride particles such as silicon nitride particles and boron nitride particles; carbide particles such as silicon carbide particles and boron carbide particles; diamond particles; carbonates such as calcium carbonate and barium carbonate, and the like.
• oxide particles such as silica particles, alumina particles, cerium oxide particles, chromium oxide particles, titanium dioxide particles, zirconium oxide particles, magnesium oxide particles, manganese dioxide particles, zinc oxide particles, and red iron oxide particles
• nitride particles such as silicon nitride particles and boron nitride particles
• carbide particles such as silicon carbide particles and boron carbide particles
• diamond particles carbonates such as calcium carbonate and barium carbonate,
• Colloidal silica can be produced by a sodium silicate method or a sol-gel method. Either method can be used to produce colloidal silica. However, from the viewpoint of reducing metal impurities, colloidal silica produced by the sol-gel method is preferred. Colloidal silica produced by the sol-gel method is preferred because it contains less metal impurities and corrosive ions such as chloride ions that have the property of diffusing in semiconductors. Colloidal silica can be produced by the sol-gel method using a conventionally known method. Specifically, colloidal silica can be obtained by hydrolysis and condensation reaction using a hydrolyzable silicon compound (e.g., alkoxysilane or its derivative) as a raw material. Commercially available colloidal silica may be used.
• a hydrolyzable silicon compound e.g., alkoxysilane or its derivative
• the shape of the abrasive grains is not particularly limited, and may be spherical or non-spherical.
• specific examples of non-spherical shapes include polygonal prisms such as triangular prisms and square prisms, cylinders, bale shapes in which the center of a cylinder is more bulging than the ends, donut shapes with a disk that is penetrated through the center, plate shapes, so-called cocoon shapes with a constriction in the center, so-called associative spheres in which multiple particles are integrated, so-called confetti shapes with multiple protrusions on the surface, and rugby ball shapes, and various other shapes are not particularly limited.
• the average value of the long axis/short axis ratio of the abrasive grains is in principle 1.0 or more, preferably 1.05 or more, and more preferably 1.1 or more. By increasing the average aspect ratio, a higher polishing rate can be achieved. Furthermore, from the viewpoint of reducing scratches, etc., the average aspect ratio of the abrasive grains is preferably 3.0 or less, more preferably 2.0 or less, and even more preferably 1.5 or less.
• the shape (outer shape) and average aspect ratio of the abrasive grains can be determined, for example, by observation with an electron microscope.
• a specific procedure for determining the average aspect ratio is, for example, to use a scanning electron microscope (SEM) to draw the smallest rectangle circumscribing each particle image for a predetermined number (e.g., 200) of silica particles whose individual particle shapes can be recognized. Then, for the rectangle drawn for each particle image, the long side length (long axis value) is divided by the short side length (short axis value) to calculate the long axis/short axis ratio (aspect ratio).
• the average aspect ratio can be found by arithmetically averaging the aspect ratios of the above-mentioned predetermined number of particles.
• the abrasive grains contained in the polishing composition may be in the form of primary particles, or in the form of secondary particles formed by aggregation of multiple primary particles. Abrasive grains in the form of primary particles and abrasive grains in the form of secondary particles may be mixed. In a preferred embodiment, at least a portion of the abrasive grains are contained in the polishing composition in the form of secondary particles.
• the surface of the object to be polished is generally finished to a high-quality mirror surface through a lapping process and a polishing process.
• the polishing process is usually composed of multiple polishing processes including a preliminary polishing process (preliminary polishing process, a polishing process before the final polishing process) and a final polishing process (final polishing process).
• a polishing composition with high processing power (polishing power) is used in the stage of roughly polishing the object to be polished (particularly silicon wafers) (e.g., preliminary polishing process), and a polishing composition with low polishing power tends to be used in the stage of more delicate polishing (e.g., final polishing process).
• the polishing composition used has different polishing characteristics required for each polishing process, so the particle size and content of silica contained in the polishing composition can be different depending on the stage of the polishing process in which the polishing composition is used.
• an increase in the particle size of the abrasive grains makes it easier to mechanically polish the surface of the object to be polished, and the polishing speed tends to increase.
• a decrease in the particle size of the abrasive grains tends to improve the surface quality of the object to be polished after polishing.
• the average primary particle size of the abrasive grains contained in the polishing composition according to some embodiments of the present invention is not particularly limited, but is preferably 5 nm or more, more preferably 10 nm or more, even more preferably 15 nm or more, and particularly preferably 20 nm or more (e.g., more than 20 nm).
• the average primary particle size of the abrasive grains contained in the polishing composition according to some embodiments of the present invention is, for example, 100 nm or less, may be 80 nm or less, preferably 60 nm or less, more preferably 50 nm or less, even more preferably 45 nm or less, and particularly preferably 43 nm or less.
• the average primary particle size of the abrasive grains may be less than 42 nm, may be less than 41 nm, may be less than 38 nm, may be less than 36 nm, may be less than 35 nm, may be less than 33 nm, or may be less than 30 nm.
• the average secondary particle diameter of the abrasive grains contained in the polishing composition according to some embodiments of the present invention is preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, and particularly preferably 35 nm or more.
• the average secondary particle diameter of the abrasive grains may be 40 nm or more, 42 nm or more, or 44 nm or more.
• the average secondary particle diameter of the abrasive grains contained in the polishing composition according to some embodiments of the present invention is, for example, 250 nm or less, 180 nm or less, 150 nm or less, preferably 100 nm or less, more preferably 90 nm or less, and even more preferably 80 nm or less.
• the average secondary particle diameter of the abrasive grains may be 70 nm or less, 60 nm or less, or 50 nm or less.
• the preferred ranges for the average primary particle size and average secondary particle size of the abrasive grains described above are also the preferred ranges for the average primary particle size and average secondary particle size of the abrasive grains contained in the raw material dispersion liquid used in its preparation.
• the specific surface area can be measured, for example, using a "Flow SorbII 2300" manufactured by Micromeritics.
• the average secondary particle size of the abrasive grains is measured, for example, by dynamic light scattering, for example, using a "Nanotrack (registered trademark) UPA-UT151" manufactured by Nikkiso Co., Ltd.
• the polishing composition used has different polishing properties required for each polishing process, so the content of abrasive grains in the polishing composition may vary depending on the stage of the polishing process at which the polishing composition is used.
• an increase in the abrasive content tends to improve the polishing speed for the surface of the object to be polished.
• a decrease in the abrasive content tends to improve the dispersion stability of the polishing composition and reduce the amount of abrasive residue on the polished surface.
• the content of abrasive grains in the concentrated liquid is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.025% by mass or more, even more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, even more particularly preferably 1% by mass or more, and most preferably 3% by mass or more.
• the content of abrasive grains in the concentrated liquid of the polishing composition is not particularly limited, but from the viewpoints of storage stability, filterability, etc., it is preferably 50% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 9% by mass or less.
• the content of the abrasive grains in the polishing composition is not particularly limited, but from the viewpoint of further improving the polishing rate, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.025% by mass or more, and particularly preferably 0.1% by mass or more.
• the content of the abrasive grains in the polishing composition is not particularly limited, but may be, for example, less than 10% by mass, less than 7% by mass, 5% by mass or less, 2% by mass or less, preferably less than 1% by mass, more preferably 0.8% by mass or less, even more preferably 0.6% by mass or less, particularly preferably 0.4% by mass or less, and most preferably 0.3% by mass or less.
• the content of abrasive grains is within the above range, compound ⁇ and the water-soluble polymer act more effectively on the surface of the object to be polished, and defects on the surface of the object to be polished can be further reduced. If the polishing composition contains two or more types of abrasive grains, the content of abrasive grains refers to the total amount of these.
• the preferred abrasive grain content is preferably adjusted by diluting a concentrated polishing composition with a dispersion medium such as water, or a solution or dispersion containing an optional polishing aid.
• the polishing composition according to some embodiments of the present invention may contain silica and other abrasive grains other than silica.
• the content of the other abrasive grains is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less, based on the total mass of the silica and the other abrasive grains.
• the most preferred form is one in which the content of the other abrasive grains is 0% by mass, i.e., a form that does not contain any other abrasive grains other than silica.
• the polishing composition according to this embodiment contains a compound ⁇ having a polyethylene oxide structure and a polypropylene oxide structure in the molecule.
• the polyethylene oxide structure is represented by "-(CH 2 CH 2 -O) n -" (n represents the number of moles added and is an integer of 2 or more) and has a group derived from ethylene oxide (oxyethylene group) (-CH 2 CH 2 -O-) as a repeating unit.
• the polypropylene oxide structure is represented by "-(CH(CH 3 )CH 2 -O) m -" (m represents the number of moles added and is an integer of 2 or more) and has a group derived from propylene oxide (oxypropylene group) (-CH(CH 3 )CH 2 -O-) as a repeating unit.
• m represents the number of moles added and is an integer of 2 or more
• propylene oxide oxypropylene group
• EO ethylene oxide
• PO propylene oxide
• the compound ⁇ may have a repeating unit having a group derived from ethylene oxide (EO) and a group derived from propylene oxide (PO), and examples thereof include a block copolymer of EO and PO, a random copolymer of EO and PO, and ethylenediaminetetrapolyoxyethylenepolyoxypropylene (poloxamine).
• the block copolymer of EO and PO may be a diblock or triblock copolymer containing a polyethylene oxide (PEO) block and a polypropylene oxide (PPO) block.
• the above triblock copolymers include PEO-PPO-PEO type triblock copolymers and PPO-PEO-PPO type triblock copolymers. In the present invention, from the viewpoint of reducing defects on the surface of the object to be polished, PEO-PPO-PEO type triblock copolymers are more preferable.
• the molar ratio EO:PO of EO and PO constituting compound ⁇ is preferably 50:50 to 98:2, more preferably 60:40 to 95:15, and even more preferably 70:30 to 90:10.
• compound ⁇ is a PEO-PPO-PEO triblock.
• compound ⁇ has the following structure (1):
• R 1 O represents an oxyethylene (-CH 2 CH 2 -O-) group
• R 2 O represents an oxypropylene (-CH(CH 3 )CH 2 -O-) group
• b represents the number of moles of R 2 O and is an integer of 2 or more and 1000 or less
• the molar ratio of R 1 O and R 2 O, (a+c):b is 70:30 to 90:10.
• the weight average molecular weight (Mw) of the compound ⁇ is preferably 100 to 10,000, more preferably 150 to 8,000, even more preferably 200 to 5,000, particularly preferably 250 to 4,500, and most preferably 300 to 4,000. In one embodiment, the weight average molecular weight of the compound ⁇ is 3500 or less. If the weight average molecular weight of the compound ⁇ is within the above range, the compound ⁇ and the water-soluble polymer act more effectively on the surface of the object to be polished, and defects on the surface of the object to be polished can be further reduced.
• the weight average molecular weight of the compound ⁇ can be a molecular weight calculated from a value based on aqueous gel permeation chromatography (GPC) (aqueous, polyethylene oxide equivalent).
• GPC gel permeation chromatography
• HLC-8320GPC aqueous, polyethylene oxide equivalent
• the measurement can be performed, for example, under the following measurement condition 1. The same method is also used for the examples described later. If the molecular weight cannot be measured by GPC, the molecular weight calculated from the molecular formula can be used as the weight average molecular weight.
• compound ⁇ may be used alone or in a mixture of two or more kinds.
• compound ⁇ may be a commercially available product or a synthetic product.
• the content (concentration) of compound ⁇ in the polishing composition is 0.0001 mass% or more, based on the total mass of the polishing composition. If the content (concentration) of compound ⁇ is less than 0.0001 mass%, compound ⁇ cannot act sufficiently on the surface of the object to be polished, and the number of defects on the surface of the object to be polished cannot be reduced.
• the content (concentration) of compound ⁇ is preferably 0.0002 mass% or more, more preferably 0.0003 mass% or more, even more preferably 0.0005 mass% or more, particularly preferably 0.0008 mass% or more, and most preferably 0.001 mass% or more, based on the total mass of the polishing composition.
• the upper limit of the content (concentration) of compound ⁇ in the polishing composition is preferably 5 mass% or less, more preferably 1 mass% or less, even more preferably 0.5 mass% or less, particularly preferably 0.2 mass% or less, and most preferably 0.1 mass% or less, based on the total mass of the polishing composition.
• the content (concentration) of compound ⁇ is preferably 0.0002 mass% or more and 5 mass% or less, more preferably 0.0003 mass% or more and 1 mass% or less, even more preferably 0.0005 mass% or more and 0.5 mass% or less, particularly preferably 0.0008 mass% or more and 0.2 mass% or less, and most preferably 0.001 mass% or more and 0.1 mass% or less, based on the total mass of the polishing composition.
• the content (concentration) of compound ⁇ in the polishing composition may be 0.001 mass% or more and 0.01 mass% or less, or may be 0.001 mass% or more and 0.005 mass% or less.
• the content (concentration) of compound ⁇ in the polishing composition may be 0.001 mass% or more and less than 0.005 mass%, may be 0.001 mass% or more and 0.004 mass% or less, or may be 0.001 mass% or more and 0.003 mass% or less.
• the polishing composition according to some embodiments of the present invention is in the form of a concentrated liquid that is diluted with a dispersion medium or the like and used for polishing
• the content (concentration) of compound ⁇ in the concentrated liquid may be 0.001% by mass or more and 10% by mass or less, 0.005% by mass or more and 1% by mass or less, 0.008% by mass or more and 0.25% by mass or less, or 0.01% by mass or more and 0.1% by mass or less.
• the content (concentration) of compound ⁇ is within this range, compound ⁇ and the water-soluble polymer act more effectively on the surface of the object to be polished, and defects on the surface of the object to be polished can be further reduced.
• the content (concentration) of compound ⁇ refers to the total amount of these.
• the compound ⁇ is contained such that the mass (total mass) of the compound ⁇ and the water-soluble polymer described later is a specific ratio to the mass of the abrasive grains. That is, in the polishing composition of this embodiment, the ratio of the total mass of the compound ⁇ (B) and the water-soluble polymer (C) to the mass of the abrasive grains (A) [ ⁇ (B) + (C) ⁇ / (A)] is 0.058 or more and less than 0.150.
• the "ratio of the total mass of the compound ⁇ (B) and the water-soluble polymer (C) to the mass of the abrasive grains (A)” may be referred to as the "mass ratio of the compound ⁇ and the water-soluble polymer to the abrasive grains".
• the mass ratio of the compound ⁇ and the water-soluble polymer to the abrasive grains is less than 0.058, the compound ⁇ and the water-soluble polymer cannot sufficiently cover the entire surface of the object to be polished, the action of the compound ⁇ and the water-soluble polymer on the surface of the object to be polished is not sufficiently exerted, and the number of defects on the surface of the object to be polished cannot be reduced.
• the mass ratio of compound ⁇ and water-soluble polymer to abrasive grains is preferably 0.059 or more, more preferably 0.060 or more, even more preferably 0.062 or more, particularly preferably 0.065 or more, and most preferably 0.068 or more.
• the mass ratio of compound ⁇ and water-soluble polymer to abrasive grains is preferably 0.140 or less, more preferably 0.120 or less, even more preferably 0.100 or less, particularly preferably 0.095 or less, and most preferably 0.090 or less.
• the polishing composition according to the present embodiment contains a water-soluble polymer different from the compound ⁇ .
• the compound ⁇ excluded from the water-soluble polymer has an EO structure and a PO structure. Therefore,
• the water-soluble polymer includes a water-soluble polymer having only either an EO structure or a PO structure.
• water-soluble means that the solubility in water (25°C) is 1 g/100 mL or more
• polymer means a (co)polymer having a weight average molecular weight of 0.5 x 104 or more.
• Any water-soluble polymer other than compound ⁇ having an EO structure and a PO structure may be used, and one having at least one functional group selected from the group consisting of cationic groups, anionic groups, and nonionic groups in the molecule may be used.
• Examples include water-soluble polymers having anionic groups, water-soluble polymers having cationic groups, and water-soluble polymers having nonionic groups.
• an anionic group refers to a functional group that becomes an anion when a counter ion dissociates.
• a cationic group refers to a functional group that becomes a cation when a counter ion dissociates or when it bonds with a cationic species generated by ionization of another ionic compound.
• a nonionic group refers to a functional group that does not ionize.
• Cationic groups are not particularly limited, but examples thereof include amino groups or salts thereof.
• water-soluble polymers having cationic groups include cationic cellulose, cationic guar gum, polydimethyldimethylenepyrrolidinium chloride, dimethyldimethylenepyrrolidinium chloride-(meth)acrylamide copolymers, (meth)acrylamide-(meth)acrylic acid-dimethyldiallylammonium chloride copolymers, polymers of N,N-dimethylaminoethyl diethyl(meth)acrylate sulfate, and N,N-dimethyl polyethylene glycol(meth)acrylate.
• anionic groups include carboxy groups, sulfo groups, phosphonic acid groups, and salts of these groups.
• water-soluble polymers having a carboxy group or a salt thereof examples include poly(meth)acrylic acid and derivatives thereof, as well as salts thereof.
• polymers having sulfo groups or salt groups include sulfonic acid-modified polyvinyl alcohol (sulfonic acid group-containing polyvinyl alcohol, sulfonic acid group-containing modified polyvinyl alcohol), sulfonic acid group-containing polystyrenes such as polystyrene sulfonic acid (sulfonic acid group-containing modified polystyrene), sulfonic acid-modified polyvinyl acetates (sulfonic acid group-containing polyvinyl acetate, sulfonic acid group-containing modified polyvinyl acetate), sulfonic acid group-containing polyesters (sulfonic acid group-containing modified polyesters), copolymers of (meth)acrylic acid-sulfonic acid group-containing monomers and sulfonic acid group-containing monomers such as copolymers of (meth)acrylic acid and sulfonic acid group-containing water-soluble polymers)
• Further examples include (co)polymers containing structural units constituted by monomers such as (meth)acryloyloxymethyl phosphate, (meth)acryloyloxyethyl phosphate, (meth)acryloyloxypropyl phosphate, (meth)acryloyloxybutyl phosphate, (meth)acryloyloxypentyl phosphate, (meth)acryloyloxyhexyl phosphate, (meth)acryloyloxyoctyl phosphate, (meth)acryloyloxydecyl phosphate, (meth)acryloyloxylauryl phosphate, (meth)acryloyloxystearyl phosphate, (meth)acryloyloxy-1,4-dimethylcyclohexyl phosphate, and derivatives thereof, as well as salts thereof.
• monomers such as (meth)acryloyloxymethyl phosphate, (meth)acryloyloxyethy
• co)polymer refers to a copolymer or a homopolymer.
• monomers constituting the structural units of the (co)polymer other than the above-mentioned structural units include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, phenylstyrene, cyclohexylstyrene, and benzylstyrene; hydroxy group-containing vinyl monomers such as hydroxystyrene, N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, and 2-hydroxyethylpropenyl ether; and alkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acryl
• water-soluble polymers having nonionic groups include compounds that contain hydroxyl groups, acyloxy groups, vinyl structures, polyoxyalkylene structures, heterocyclic structures, amide structures, imide structures, etc. in the molecule.
• water-soluble polymers having nonionic groups include vinyl alcohol polymers, polymers containing oxyalkylene units (excluding compound ⁇ having an EO structure and a PO structure), cellulose derivatives, starch derivatives, nitrogen atom-containing polymers, etc.
• the vinyl alcohol polymer refers to a polymer having a vinyl alcohol unit (a structural portion represented by -CH 2 -CH(OH)-; hereinafter also referred to as "VA unit”) in one molecule.
• the vinyl alcohol polymer may be a copolymer containing a non-vinyl alcohol unit (a structural unit derived from a monomer other than vinyl alcohol, hereinafter also referred to as "non-VA unit”) in addition to the VA unit.
• the non-VA unit has at least one structure selected from an oxyalkylene group, a carboxy group, a (di)carboxylic acid group, a (di)carboxylic acid ester group, a phenyl group, a naphthyl group, a sulfo group, an amino group, a hydroxyl group, an amide group, an imide group, a nitrile group, an ether group, an ester group, and a salt thereof.
• non-VA unit examples are not particularly limited, and may be a repeating unit derived from an N-vinyl type monomer or an N-(meth)acryloyl type monomer, a repeating unit derived from ethylene, a repeating unit derived from an alkyl vinyl ether, a repeating unit derived from a vinyl ester of a monocarboxylic acid having 3 or more carbon atoms, and the like, but are not limited thereto.
• a suitable example of the N-vinyl type monomer is N-vinylpyrrolidone.
• a suitable example of the N-(meth)acryloyl type monomer is N-(meth)acryloylmorpholine.
• the alkyl vinyl ether may be a vinyl ether having an alkyl group having 1 to 10 carbon atoms, such as propyl vinyl ether, butyl vinyl ether, or 2-ethylhexyl vinyl ether.
• the vinyl ester of a monocarboxylic acid having 3 or more carbon atoms may be a vinyl ester of a monocarboxylic acid having 3 to 7 carbon atoms, such as vinyl propanoate, vinyl butanoate, vinyl pentanoate, or vinyl hexanoate.
• Suitable examples of the (di)acetone compound include diacetone (meth)acrylamide and acetylacetone.
• the vinyl alcohol polymer When the vinyl alcohol polymer contains a non-VA unit, it may contain only one type of non-VA unit, or may contain two or more types of non-VA units.
• the content ratio (molar ratio) of VA units to non-VA units is not particularly limited, and for example, the VA units:non-VA units (molar ratio) is preferably 1:99 to 99:1, and more preferably 95:5 to 50:50.
• vinyl alcohol-based polymers include polyvinyl alcohol (PVA), vinyl alcohol-ethylene copolymers, and acetalized polyvinyl alcohol.
• Acetalized polyvinyl alcohol is a vinyl alcohol-based polymer in which a portion of the VA units contained in polyvinyl alcohol is acetalized with an aldehyde.
• the degree of saponification of polyvinyl alcohol is not particularly limited, but is preferably 80% or more and 100% or less, more preferably 90% or more and 100% or less, even more preferably 95% or more and 100% or less, and particularly preferably 98% or more and 100% or less.
• a polymer having an oxyalkylene unit refers to a polymer containing a (poly)oxyalkylene group (excluding compound ⁇ having an EO structure and a PO structure).
• a (poly)oxyalkylene group refers to an oxyalkylene group or a polyoxyalkylene group.
• polymers having an oxyalkylene unit include polyalkylene oxides such as polyethylene oxide (PEO) and polypropylene oxide (PPO); various polyalkylene glycol alkyl ethers such as polyethylene glycol oleyl ether and polyethylene glycol dimethyl ether; and polyalkylene glycol alkyl esters such as polyethylene glycol monooctyl ester, polypropylene glycol monostearyl ester, and polypropylene glycol distearyl ester.
• polyalkylene oxides such as polyethylene oxide (PEO) and polypropylene oxide (PPO)
• various polyalkylene glycol alkyl ethers such as polyethylene glycol oleyl ether and polyethylene glycol dimethyl ether
• polyalkylene glycol alkyl esters such as polyethylene glycol monooctyl ester, polypropylene glycol monostearyl ester, and polypropylene glycol distearyl ester.
• Cellulose derivatives are cellulose in which some of the hydroxyl groups have been replaced with other different substituents.
• examples of cellulose derivatives include hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and carboxymethyl cellulose.
• Starch derivatives are starch or starch in which some of the hydroxyl groups have been replaced with other different substituents. Examples of starch derivatives include pullulan.
• Nitrogen atom-containing polymers include, for example, polymers containing N-vinyl type monomer units; polymers containing N-(meth)acryloyl type monomer units; and the like.
• N-vinyl type polymers include polymers containing repeating units derived from monomers having nitrogen-containing heterocycles (e.g., lactam rings).
• polymers examples include homopolymers and copolymers of N-vinyl lactam type monomers (e.g., copolymers in which the copolymerization ratio of N-vinyl lactam type monomers exceeds 50% by mass), homopolymers and copolymers of N-vinyl chain amides (e.g., copolymers in which the copolymerization ratio of N-vinyl chain amides exceeds 50% by mass), and the like.
• N-vinyl lactam type monomers e.g., copolymers in which the copolymerization ratio of N-vinyl lactam type monomers exceeds 50% by mass
• N-vinyl chain amides e.g., copolymers in which the copolymerization ratio of N-vinyl chain amides exceeds 50% by mass
• N-vinyl lactam type monomers i.e., compounds having a lactam structure and an N-vinyl group in one molecule
• N-vinyl pyrrolidone VP
• N-vinyl piperidone N-vinyl morpholinone
• N-vinyl caprolactam VC
• N-vinyl-1,3-oxazin-2-one N-vinyl-3,5-morpholinedione.
• N-(meth)acryloyl type polymers include homopolymers and copolymers of N-(meth)acryloyl type monomers (typically copolymers in which the copolymerization ratio of N-(meth)acryloyl type monomers exceeds 50 mass%).
• Examples of N-(meth)acryloyl type monomers include linear amides having an N-(meth)acryloyl group and cyclic amides having an N-(meth)acryloyl group.
• chain amides having an N-(meth)acryloyl group include (meth)acrylamide; N-alkyl (meth)acrylamides such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, and N-n-butyl (meth)acrylamide; and N,N-dialkyl (meth)acrylamides such as N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, N,N-diisopropyl (meth)acrylamide, and N,N-di(n-butyl) (meth)acrylamide.
• N-alkyl (meth)acrylamides such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide
• polymers containing chain amides having an N-(meth)acryloyl group as monomer units include homopolymers of N-isopropylacrylamide and copolymers of N-isopropylacrylamide (for example, copolymers in which the copolymerization ratio of N-isopropylacrylamide exceeds 50% by mass).
• Examples of cyclic amides having an N-(meth)acryloyl group include N-acryloylmorpholine, N-acryloylthiomorpholine, N-acryloylpiperidine, N-acryloylpyrrolidine, N-methacryloylmorpholine, N-methacryloylpiperidine, N-methacryloylpyrrolidine, etc.
• An example of a polymer containing a cyclic amide having an N-(meth)acryloyl group as a monomer unit is an acryloylmorpholine-based polymer (PACMO).
• acryloylmorpholine-based polymers include homopolymers of N-acryloylmorpholine (ACMO) and copolymers of ACMO (for example, copolymers in which the copolymerization ratio of ACMO exceeds 50 mass%).
• ACMO N-acryloylmorpholine
• the ratio of the number of moles of ACMO units to the number of moles of all repeating units is usually 50% or more, and suitably 80% or more (e.g., 90% or more, typically 95% or more). All repeating units of the water-soluble polymer may be substantially composed of ACMO units.
• the salt include, but are not limited to, alkali metal salts such as sodium salts and potassium salts, salts of Group 2 elements such as calcium salts and magnesium salts, amine salts, and ammonium salts.
• the weight average molecular weight Mw of the water-soluble polymer may be, for example, about 200 ⁇ 10 4 or less, and is suitably about 150 ⁇ 10 4 or less, and from the viewpoint of cleaning properties, etc., is preferably about 100 ⁇ 10 4 or less, and may be about 50 ⁇ 10 4 or less.
• the Mw of the water-soluble polymer is preferably, for example, 0.5 ⁇ 10 4 or more.
• the Mw is suitably 1.0 ⁇ 10 4 or more, and may be 1.5 ⁇ 10 4 or more, 2 ⁇ 10 4 or more, for example, 5 ⁇ 10 4 or more.
• the preferred molecular weight range of the water-soluble polymer compound may vary depending on the type of polymer used.
• the Mw of the polyvinyl alcohol-based polymer can be 100 ⁇ 10 4 or less, and is suitably 60 ⁇ 10 4 or less. From the viewpoint of concentration efficiency, the Mw may be 30 ⁇ 10 4 or less, preferably 20 ⁇ 10 4 or less, for example, 10 ⁇ 10 4 or less, 8 ⁇ 10 4 or less, 5 ⁇ 10 4 or less, 3 ⁇ 10 4 or less, 2 ⁇ 10 4 or less, or 1.5 ⁇ 10 4 or less.
• the Mw of the polyvinyl alcohol-based polymer is small, the dispersion stability of the polyvinyl alcohol-based polymer tends to improve.
• the Mw is preferably, for example, 0.5 ⁇ 10 4 or more. In some embodiments, the Mw is suitably 0.8 ⁇ 10 4 or more, and may be 1.0 ⁇ 10 4 or more.
• the Mw of the polymer containing an oxyalkylene unit can be 10 x 10 4 or less, 5 x 10 4 or less, 3 x 10 4 or less, or 2 x 10 4 or less.
• the Mw can be 0.5 x 10 4 or more, 1 x 10 4 or more, 1.2 x 10 4 or more, or 1.5 x 10 4 or more.
• the Mw of the cellulose derivative and the starch derivative can be about 500 ⁇ 10 4 or less, and is suitably 300 ⁇ 10 4 or less.
• the Mw may be about 200 ⁇ 10 4 or less, or may be about 100 ⁇ 10 4 or less (for example, about 80 ⁇ 10 4 or less).
• the Mw is suitably, for example, about 5.0 ⁇ 10 4 or more, preferably about 10 ⁇ 10 4 or more, more preferably about 30 ⁇ 10 4 or more, even more preferably about 35 ⁇ 10 4 or more, may be about 40 ⁇ 10 4 or more, or may be about 50 ⁇ 10 4 or more. It may be about 55 ⁇ 10 4 or more.
• the Mw of the nitrogen atom-containing polymer having a cyclic structure can be 100 ⁇ 10 4 or less, and is suitably 70 ⁇ 10 4 or less.
• the Mw may be 60 ⁇ 10 4 or less, or may be 50 ⁇ 10 4 or less.
• the Mw may be, for example, 1.0 ⁇ 10 4 or more, or may be 10 ⁇ 10 4 or more.
• the Mw may be suitably 20 ⁇ 10 4 or more, and may preferably be 30 ⁇ 10 4 or more.
• the Mw of the cellulose derivatives and starch derivatives can be calculated from values based on aqueous gel permeation chromatography (GPC) (aqueous, pullulan equivalent).
• GPC gel permeation chromatography
• the GPC measuring device used can be a Tosoh Corporation model called "HLC-8320GPC.” Measurements can be performed, for example, under the following measurement condition 2. The same method is used in the examples described later.
• the Mw of water-soluble polymers other than cellulose derivatives and starch derivatives can be calculated from values based on aqueous gel permeation chromatography (GPC) (aqueous, polyethylene oxide equivalent).
• GPC gel permeation chromatography
• the GPC measurement conditions can be the same as the measurement conditions 1 for compound ⁇ described above. The same method is used in the examples described below.
• the water-soluble polymer may be used alone or in combination of two or more kinds.
• the water-soluble polymer may be a commercially available product or a synthetic product.
• the water-soluble polymer is preferably a water-soluble polymer having a hydroxyl group, and more preferably hydroxyethyl cellulose.
• the water-soluble polymer includes hydroxyethyl cellulose and poly N-acryloylmorpholine.
• the water-soluble polymer is hydroxyethyl cellulose and PACMO.
• the mass ratio of hydroxyethyl cellulose:poly N-acryloylmorpholine is preferably 70:30 to 99:1, more preferably 80:20 to 99:1, even more preferably 85:15 to 99:1, and particularly preferably 90:10 to 98:2.
• the water-soluble polymer is hydroxyethyl cellulose and poly N-acryloylmorpholine
• the mass ratio of hydroxyethyl cellulose:poly N-acryloylmorpholine is 70:30 to 99:1 (preferably 80:20 to 99:1, more preferably 85:15 to 99:1, and even more preferably 90:10 to 98:2).
• the content (concentration) of the water-soluble polymer in the concentrated liquid is not particularly limited, but is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, and even more preferably 0.01 mass% or more.
• the content (concentration) of the water-soluble polymer in the concentrated liquid of the polishing composition is not particularly limited, but is preferably 15 mass% or less, more preferably 5 mass% or less, and even more preferably 3 mass% or less, from the viewpoint of storage stability, etc.
• the content (concentration) of the water-soluble polymer is preferably 0.001 mass% or more and 15 mass% or less, more preferably 0.005 mass% or more and 5 mass% or less, and even more preferably 0.01 mass% or more and 3 mass% or less.
• the content (concentration) of the water-soluble polymer in the polishing composition is preferably 0.0001 mass% or more, more preferably 0.0003 mass% or more, even more preferably 0.0005 mass% or more, particularly preferably 0.001 mass% or more, and most preferably 0.005 mass% or more, based on the total mass of the polishing composition.
• the upper limit of the content (concentration) of the water-soluble polymer in the polishing composition is preferably 5 mass% or less, more preferably 1 mass% or less, even more preferably 0.5 mass% or less, particularly preferably 0.2 mass% or less, and most preferably 0.1 mass% or less, based on the total mass of the polishing composition.
• the content (concentration) of the water-soluble polymer is preferably 0.0001% by mass or more and 5% by mass or less, more preferably 0.0003% by mass or more and 1% by mass or less, even more preferably 0.0005% by mass or more and 0.5% by mass or less, particularly preferably 0.001% by mass or more and 0.2% by mass or less, and most preferably 0.005% by mass or more and 0.1% by mass or less, relative to the total mass of the polishing composition.
• the content (concentration) of the water-soluble polymer in the polishing composition may be 0.001% by mass or more and 0.05% by mass or less, or may be 0.005% by mass or more and 0.05% by mass or less.
• the polishing composition according to the present embodiment contains a basic compound.
• the basic compound refers to a compound that has the function of increasing the pH of water when added to water.
• the type of basic compound is not particularly limited, but examples include organic or inorganic basic compounds containing nitrogen, hydroxides of alkali metals or Group 2 metals, various carbonates and bicarbonates, quaternary ammonium or its salts, ammonia, amines, etc.
• alkali metal hydroxides include potassium hydroxide and sodium hydroxide.
• Group 2 metal hydroxides include calcium hydroxide, strontium hydroxide, barium hydroxide, etc.
• Specific examples of carbonates or bicarbonates include ammonium bicarbonate, ammonium carbonate, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, etc.
• quaternary ammonium or its salts include quaternary ammonium hydroxides such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, and tetrabutylammonium hydroxide.
• TMAH tetramethylammonium hydroxide
• tetraethylammonium hydroxide tetraethylammonium hydroxide
• tetrabutylammonium hydroxide tetrabutylammonium hydroxide
• amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-( ⁇ -aminoethyl)ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, anhydrous piperazine, piperazine hexahydrate, 1-(2-aminoethyl)piperazine, N-methylpiperazine, guanidine, and azoles such as imidazole and triazole.
• the basic compound is preferably at least one selected from the group consisting of ammonia, quaternary ammonium (preferably quaternary ammonium hydroxide), carbonates, hydrogen carbonates, and hydroxides of alkali metals.
• the basic compound may be used alone or in combination of two or more.
• the basic compound may be a commercially available product or a synthetic product.
• the content (concentration) of the basic compound in the concentrated liquid is not particularly limited, but is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, even more preferably 0.01 mass% or more, and particularly preferably 0.05 mass% or more.
• the content (concentration) of the basic compound in the concentrated liquid of the polishing composition is not particularly limited, but from the viewpoint of storage stability, etc., it is preferably 45 mass% or less, more preferably 15 mass% or less, even more preferably 5 mass% or less, and particularly preferably 1 mass% or less.
• the content (concentration) of the basic compound is preferably 0.001 mass% or more and 45 mass% or less, more preferably 0.005 mass% or more and 15 mass% or less, even more preferably 0.01 mass% or more and 5 mass% or less, and particularly preferably 0.05 mass% or more and 1 mass% or less.
• the content (concentration) of the basic compound in the polishing composition is not particularly limited, but from the viewpoint of improving the polishing removal rate, etc., it is preferably 0.0001 mass% or more, more preferably 0.0005 mass% or more, even more preferably 0.001 mass% or more, even more preferably 0.002 mass% or more, and particularly preferably 0.003 mass% or more, based on the total mass of the polishing composition.
• the content (concentration) of the basic compound in the polishing composition is not particularly limited, but from the viewpoint of improving surface quality, such as reducing defects, it is preferably 15 mass% or less, more preferably 10 mass% or less, even more preferably 5 mass% or less, even more preferably 1 mass% or less, and particularly preferably 0.5 mass% or less, based on the total mass of the polishing composition.
• the content (concentration) of the basic compound in the polishing composition is preferably 0.0001% by mass or more and 15% by mass or less, more preferably 0.0005% by mass or more and 10% by mass or less, even more preferably 0.001% by mass or more and 5% by mass or less, even more preferably 0.002% by mass or more and 1% by mass or less, and particularly preferably 0.003% by mass or more and 0.5% by mass or less.
• the pH of the polishing composition according to this embodiment is preferably 7.0 or more, more preferably 7.5 or more, even more preferably 8.0 or more, particularly preferably 8.5 or more, and most preferably 9.0 or more.
• the pH of the polishing composition is preferably 12.5 or less, more preferably 12.0 or less, even more preferably 11.5 or less, particularly preferably 11.0 or less, and most preferably 10.5 or less. That is, the pH of the polishing composition is preferably 7.0 or more and 12.5 or less, more preferably 7.5 or more and 12.0 or less, even more preferably 8.0 or more and 11.5 or less, particularly preferably 8.5 or more and 11.0 or less, and most preferably 9.0 or more and 10.5 or less.
• the pH of the polishing composition is 9.5 or more and 11.0 or less. If the pH of the polishing composition is in such a range, the compound ⁇ and the water-soluble polymer act more effectively on the surface of the object to be polished, and defects on the surface of the object to be polished can be further reduced.
• the content of the pH adjuster can be selected by appropriately adjusting it within the range in which the effects of the present invention are achieved.
• the pH of the polishing composition can be measured, for example, with a pH meter (for example, a pH meter (model number: LAQUA) manufactured by Horiba, Ltd.).
• the polishing composition according to the present embodiment contains a dispersion medium for dispersing each component.
• the dispersion medium particularly water has the function of dissolving or dispersing the components contained in the polishing composition.
• the dispersion medium may be a mixed solvent of water and an organic solvent for dispersing or dissolving each component.
• organic solvent examples include acetone, acetonitrile, ethanol, methanol, isopropanol, glycerin, ethylene glycol, propylene glycol, etc., which are organic solvents miscible with water.
• these organic solvents may be used without mixing with water, and then each component may be dispersed or dissolved, and then mixed with water. These organic solvents may be used alone or in combination of two or more.
• the dispersion medium contains water.
• the dispersion medium is substantially composed of water.
• the above term “substantially” means that a dispersion medium other than water may be included, as long as the effects of the present invention can be achieved. More specifically, the dispersion medium is preferably composed of 90% by mass to 100% by mass of water and 0% by mass to 10% by mass of a dispersion medium other than water, and more preferably composed of 99% by mass to 100% by mass of water and 0% by mass to 1% by mass of a dispersion medium other than water. According to the most preferred embodiment of this embodiment, the dispersion medium is only water.
• the water contains as few impurities as possible.
• water with a total transition metal ion content of 100 ppb or less is preferable.
• the purity of the water can be increased by, for example, removing impurity ions using ion exchange resin, removing foreign matter using a filter, distillation, or other operations.
• the polishing composition according to this embodiment may further contain known additives that can be used in polishing compositions, such as a chelating agent (complexing agent), a pH adjuster, a fungicide (preservative), and a surfactant (excluding the above-mentioned compound ⁇ ), within a range that does not inhibit the effects of the present invention.
• a chelating agent complexing agent
• a pH adjuster pH adjuster
• a fungicide preservative
• surfactant excluding the above-mentioned compound ⁇
• the chelating agent, the pH adjuster, the fungicide (preservative), and the surfactant will be described below.
• the oxidizing agent will also be described.
• the chelating agent captures metal impurity components in the polishing system to form a complex, thereby suppressing metal contamination on the surface of the object to be polished.
• the polishing composition according to one embodiment of this aspect may further contain a chelating agent.
• chelating agents include aminocarboxylic acid chelating agents and organic phosphonic acid chelating agents.
• aminocarboxylic acid chelating agents include ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, nitrilotriacetic acid, sodium nitrilotriacetate, ammonium nitrilotriacetate, hydroxyethylethylenediaminetriacetic acid, sodium hydroxyethylethylenediaminetriacetate, diethylenetriaminepentaacetic acid, sodium diethylenetriaminepentaacetate, triethylenetetraminehexaacetic acid, and sodium triethylenetetraminehexaacetate.
• organic phosphonic acid chelating agents include 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), ethane-1,1,-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, ⁇ -methylphosphonosuccinic acid, etc.
• organic phosphonic acid chelating agent in particular ethylenediaminetetra
• the pH can be adjusted by each component described above, but the pH can also be adjusted to a desired pH by using a pH adjuster.
• the polishing composition of this embodiment may further contain a pH adjuster.
• the pH adjuster may include compounds other than the basic compounds described above, such as inorganic acids and organic acids.These may be used alone or in combination of two or more.
• inorganic acids that can be used as pH adjusters include hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, and phosphoric acid.
• hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid are preferred, and nitric acid is more preferred.
• salts such as alkali metal salts of inorganic or organic acids may be used in place of or in combination with inorganic or organic acids.
• a pH buffering effect can be expected.
• the antifungal agent is not particularly limited and can be appropriately selected depending on the desired use and purpose. Specific examples include isothiazoline preservatives such as 1,2-benzisothiazol-3(2H)-one (BIT), 2-methyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one, and phenoxyethanol.
• isothiazoline preservatives such as 1,2-benzisothiazol-3(2H)-one (BIT), 2-methyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one, and phenoxyethanol.
• the surfactant may be used alone or in combination of two or more.
• examples of the surfactant are not particularly limited, and include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
• the dispersion stability of the polishing composition can be improved by using a surfactant (e.g., a water-soluble organic compound with a molecular weight of less than 0.5 ⁇ 10 4 ).
• the Mw of the surfactant can be a value determined by GPC (water-based, polyethylene oxide equivalent) or a value calculated from a chemical formula.
• the measurement conditions of GPC can be the same as those of the above-mentioned compound ⁇ .
• the polishing composition according to some embodiments of this embodiment preferably does not substantially contain an oxidizing agent. If an oxidizing agent is contained in the polishing composition, the surface of the object to be polished (especially a silicon wafer) is oxidized to form an oxide film, which increases the required polishing time.
• the oxidizing agent include hydrogen peroxide (H 2 O 2 ), sodium persulfate, ammonium persulfate, and sodium dichloroisocyanurate.
• the polishing composition "substantially does not contain an oxidizing agent" means that the oxidizing agent is not contained at least intentionally.
• a polishing composition that inevitably contains a small amount of oxidizing agent for example, the molar concentration of the oxidizing agent in the polishing composition is 0.001 mol/L or less, preferably 0.0005 mol/L or less, more preferably 0.0001 mol/L or less, even more preferably 0.00005 mol/L or less, and particularly preferably 0.00001 mol/L or less
• the molar concentration of the oxidizing agent in the polishing composition is 0.001 mol/L or less, preferably 0.0005 mol/L or less, more preferably 0.0001 mol/L or less, even more preferably 0.00005 mol/L or less, and particularly preferably 0.00001 mol/L or less
• the method for producing the polishing composition according to some embodiments of the present invention is not particularly limited.
• the polishing composition can be produced by adding abrasive grains, compound ⁇ , water-soluble polymer, basic compound, and other components added as necessary to a dispersion medium all at once or sequentially, and stirring in the dispersion medium.
• the polishing composition according to some embodiments of this aspect may be a one-liquid type or a multi-liquid type consisting of two or more liquids.
• the polishing composition described above may be used for polishing as it is, or may be prepared by adding water to dilute the concentrated solution of the polishing composition, or in the case of a multi-agent type polishing composition, diluting it with an aqueous solution containing water and a part of the constituents, and then used for polishing.
• the concentrated solution of the polishing composition can be stored or transported, and then diluted at the time of use to prepare the polishing composition.
• a concentrated solution of the polishing composition according to this aspect is also provided (the polishing composition according to this aspect may be in the form of a concentrated solution).
• a polishing composition in concentrated form is advantageous from the standpoint of convenience and cost reduction during production, distribution, storage, etc.
• the concentration ratio can be, for example, about 2 to 100 times in volume terms, and is usually about 5 to 50 times.
• the concentration ratio of the polishing composition (concentrate) in a preferred embodiment is 10 to 40 times, for example, 15 to 30 times.
• the object to be polished using the polishing composition according to some embodiments of the present invention is not particularly limited, and can be applied to the polishing of objects of various materials and shapes.
• the material of the object to be polished can be, for example, silicon material, aluminum, nickel, tungsten, steel, tantalum, titanium, stainless steel, or other metals or semimetals, or their alloys; glassy materials such as quartz glass, aluminosilicate glass, and glassy carbon; ceramic materials such as alumina, silica, sapphire, silicon nitride, tantalum nitride, and titanium carbide; compound semiconductor substrate materials such as silicon carbide, gallium nitride, and gallium arsenide; resin materials such as polyimide resin; and the like.
• the object to be polished can be made up of a plurality of the above-mentioned materials.
• the polishing composition according to some embodiments of the present invention is preferably used to polish a substrate having a surface made of a silicon material.
• the silicon material preferably contains at least one material selected from the group consisting of silicon single crystal, amorphous silicon, and polysilicon. From the viewpoint of obtaining the effects of the present invention more significantly, the silicon material is more preferably silicon single crystal or polysilicon, and particularly preferably silicon single crystal.
• the polishing composition according to some embodiments of the present invention is particularly preferably used for polishing a substrate (e.g., a silicon wafer) having a surface made of silicon single crystal. In other words, the polishing composition according to this embodiment is preferably used for polishing an object to be polished that contains a silicon material.
• the silicon wafer polished using the polishing composition of this embodiment may be either p-type or n-type. There is also no particular restriction on the crystal orientation of the silicon wafer, and it may be any of ⁇ 100>, ⁇ 110>, or ⁇ 111>.
• the shape of the object to be polished is not particularly limited.
• the polishing composition according to some embodiments of the present invention can be preferably applied to polishing objects having flat surfaces, such as plate-shaped or polyhedral objects.
• polishing method comprising polishing an object to be polished using the polishing composition.
• a polishing method comprising a step of polishing an object to be polished containing a silicon material using the polishing composition.
• the polishing composition according to this embodiment is particularly suitable for use in a final polishing step, since it has an excellent effect of reducing defects on the surface of the object to be polished. That is, the polishing method according to some embodiments of the present invention is suitable for use in a final polishing step.
• a manufacturing method of an object to be polished including a final polishing step using the polishing composition is also provided.
• the final polishing step refers to the last polishing step in the manufacturing process of the object (i.e., a step in which no further polishing is performed after the step).
• the polishing composition according to some embodiments of the present invention may also be used in a polishing step upstream of the final polishing step (a step between the rough polishing step and the final polishing step), for example, a polishing step performed immediately before the final polishing step.
• the polishing composition according to some embodiments of the present invention is preferably used for polishing silicon wafers.
• the polishing composition according to some embodiments of the present invention is particularly suitable as a polishing composition used in the finish polishing process of silicon wafers. More specifically, the polishing composition according to some embodiments of the present invention is suitable for use in polishing silicon wafers that have been prepared to a surface state with a surface roughness of 0.01 nm or more and 100 nm or less by a process upstream of the finish polishing process.
• a general polishing device can be used that is equipped with a holder for holding a substrate or the like having an object to be polished, a motor that can change the rotation speed, and a polishing platen onto which a polishing pad (polishing cloth) can be attached.
• the polishing pad may be of any type, including general nonwoven fabric, polyurethane, suede, etc., without any particular restrictions. It is preferable that the polishing pad has grooves formed therein so that the polishing composition can accumulate.
• the polishing conditions are set appropriately depending on the stage of the polishing process in which the polishing composition is used.
• a double-sided polishing machine or a single-sided polishing machine may be used, but a double-sided polishing machine is preferably used.
• the rotation speed of the platen is usually about 10 rpm or more and 100 rpm or less, and preferably about 20 rpm or more and 50 rpm or less.
• the rotation speeds of the upper and lower rotating platen may be different, but are usually set to the same relative speed with respect to the wafer.
• a single-sided polishing machine can be preferably used, and the rotation speed of the platen is usually about 10 rpm or more and 100 rpm or less, and preferably about 20 rpm or more and 50 rpm or less, and more preferably about 25 rpm or more and 50 rpm or less. At such a rotation speed, defects on the surface of the object to be polished can be significantly reduced.
• the object to be polished is usually pressurized by a platen.
• the pressure can be selected as appropriate, but in the preliminary polishing process, it is usually preferably about 5 kPa to 30 kPa, and more preferably about 10 kPa to 25 kPa. In the finish polishing process, it is usually preferably about 5 kPa to 30 kPa, and more preferably about 10 kPa to 20 kPa. Such a pressure can significantly reduce defects on the surface of the object to be polished.
• the supply speed of the polishing composition can also be appropriately selected depending on the size of the platen, but in terms of economy, in the case of the preliminary polishing process, it is usually preferred to be about 0.1 L/min to 5 L/min, and more preferably about 0.2 L/min to 2 L/min. In the case of the finish polishing process, it is usually preferred to be about 0.1 L/min to 5 L/min, and more preferably about 0.2 L/min to 2 L/min. With such a supply speed, the surface of the object to be polished can be polished efficiently and defects on the surface of the object to be polished can be significantly reduced.
• the temperature at which the polishing composition is held in the polishing device there are no particular limitations on the temperature at which the polishing composition is held in the polishing device, but from the standpoint of the stability of the polishing rate and the reduction of defects, a temperature of 15°C or higher and 40°C or lower is generally preferred, and 18°C or higher and 25°C or lower is even more preferred.
• polishing conditions are merely examples, and may be outside the above range, or the settings may be changed as appropriate. Such conditions can be set as appropriate by a person skilled in the art.
• SC-1 cleaning solution a mixture of ammonium hydroxide (NH 4 OH), hydrogen peroxide (H 2 O 2 ), and water (H 2 O)
• SC-2 cleaning solution a mixture of HCl, H 2 O 2 , and H 2 O
• ozone water cleaning solution a mixture of HCl, H 2 O 2 , and H 2 O
• hydrofluoric acid cleaning solution a mixture of HCl, H 2 O 2 , and H 2 O
• the temperature of the cleaning solution can be, for example, in the range of room temperature (typically about 15° C. to 25° C.) or higher, up to about 90° C.
• the present invention includes the following aspects and configurations.
• a polishing composition comprising (A) an abrasive grain, (B) a compound ⁇ having a polyethylene oxide structure and a polypropylene oxide structure, (C) a water-soluble polymer different from the compound ⁇ , (D) a basic compound, and (E) a dispersion medium, in which the compound ⁇ is contained in an amount of 0.0001 mass% or more based on the total mass of the polishing composition, and the ratio of the total mass of the compound ⁇ (B) and the water-soluble polymer (C) to the mass of the abrasive grain (A), [ ⁇ (B)+(C) ⁇ /(A)], is 0.058 or more and less than 0.150.
• a polishing method comprising a step of polishing an object containing a silicon material using the polishing composition described in any one of [1] to [8] above.
• ⁇ Average primary particle size of abrasive grains The average primary particle size of the abrasive grains was calculated from the specific surface area of the abrasive grains measured by the BET method and the density of the abrasive grains.
• the specific surface area of the abrasive grains measured by the BET method was measured using "Flow Sorb II 2300" manufactured by Micromeritics.
• ⁇ pH of Polishing Composition The pH of the polishing composition was measured using a glass electrode type hydrogen ion concentration indicator (Model: F-23, manufactured by Horiba, Ltd.). Three-point calibration was performed using the following standard buffer solutions: phthalate pH buffer solution pH: 4.01 (25° C.), neutral phosphate pH buffer solution pH: 6.86 (25° C.), and carbonate pH buffer solution pH: 10.01 (25° C.). Thereafter, the glass electrode was placed in the polishing composition for 2 minutes or more. After the pH of the polishing composition became stable, the pH of the polishing composition was measured.
• polishing compositions shown in Table 1 below were prepared using the following raw materials.
• Abrasive Grain A Colloidal silica Average primary particle diameter: 35 nm (manufactured by Fuso Chemical Co., Ltd., product name "PL-3")
• Abrasive grain b colloidal silica Average primary particle diameter: 25 nm (manufactured by Fuso Chemical Co., Ltd., product name "PL-2”)
• Water-soluble polymer Hydroxyethyl cellulose (HEC) (weight average molecular weight (Mw) 590,000)
• Poly N-acryloylmorpholine (PACMO) weight average molecular weight (Mw) 350,000)
• Example 1 The above abrasive grains b as the abrasive grains, the above EO-PO compound 1 as the compound ⁇ , the above HEC and PACMO as the water-soluble polymers, and ammonia as the basic compound were added to pure water as the dispersion medium at room temperature (25° C.) to obtain a concentrated liquid. The concentrated liquid was stirred and mixed at room temperature (25° C.) for 30 minutes, and then pure water as the dispersion medium was added to the mixed liquid at the dilution ratio shown in Table 1 to prepare the polishing composition of Example 1. The content of each component shown in Table 1 is the blend amount after dilution.
• mass ratio ((B+C)/A) represents the mass ratio of the content of compound ⁇ (B mass%) and the content of the water-soluble polymer (C mass%) to the content of the abrasive grains (A mass%).
• the pH of the obtained polishing composition was 10.1.
• Examples 2 to 10, Comparative Examples 1 to 5 Polishing compositions of Examples 2 to 10 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1, except that the types and concentrations of the components were changed as shown in Table 1 below.
• the pH of each polishing composition was 10.1.
• the particle size of the abrasive grains in each polishing composition was the same as the particle size of the abrasive grains used.
• EO-PO compound 1 was used as compound ⁇ , and only HEC was used as the water-soluble polymer.
• the surface of the silicon wafer was pre-polished under the following polishing condition 1.
• the surface of the pre-polished silicon wafer was finish-polished under the following polishing condition 2 using the polishing compositions of the Examples and Comparative Examples.
• the polished silicon wafer was removed from the polishing apparatus.
• the removed silicon wafer was cleaned using a single-wafer wafer cleaning apparatus. First, the silicon wafer was cleaned with an ozone water cleaning solution for 60 seconds, and then cleaned with an SC-1 cleaning solution and a brush for 110 seconds. Next, the silicon wafer was cleaned with an ozone water cleaning solution for 20 seconds, and then cleaned with a hydrofluoric acid cleaning solution for 15 seconds.
• the silicon wafer was subjected to a total of three sets of cleaning, with the ozone water cleaning and hydrofluoric acid cleaning being one set.
• the cleaned silicon wafer was further cleaned with an ozone water cleaning solution for 20 seconds. Thereafter, the silicon wafer was dried.
• [Polished object] Wafer A p-type COP (Crystal Organate 65d Particle)-free silicon wafer having a crystal orientation of ⁇ 100> and a size of 300 mm was prepared.
• Polishing condition 1 ⁇ Grinding machine: PNX-332B (manufactured by Okamoto Machine Tools Works, Ltd.) Polishing pad: POLYPAS275NX (manufactured by Fujibo Co., Ltd.) Polishing load: 10 kPa ⁇ Plate rotation speed: 30 rpm Carrier rotation speed: 30 rpm Polishing time: 2 min - Temperature of cooling water for surface plate: 20°C Temperature of polishing composition: 20° C.
• Polishing composition for preliminary polishing a polishing composition containing 1.0 mass % of abrasive grains (colloidal silica having an average primary particle size of 35 nm) and 0.06 mass % of potassium hydroxide in deionized water.
• polishing condition 2 polishing condition 2
• ⁇ Grinding machine PNX-332B (manufactured by Okamoto Machine Tools Works, Ltd.) Polishing pad: POLYPAS275NX (manufactured by Fujibo Co., Ltd.)
• ⁇ Polishing load 12kPa
• ⁇ Plate rotation speed 30 rpm
• Carrier rotation speed 30 rpm
• Polishing time 2 min - Temperature of cooling water for surface plate: 20°C Temperature of polishing composition: 20° C.
• Supply rate of polishing composition 1.5 L/min Polishing composition for final polishing: Polishing compositions of Examples and Comparative Examples described in Table 1.
• the polishing rate was calculated by dividing the difference in weight of the silicon wafer before and after finish polishing [(weight before polishing) - (weight after polishing)] by the polishing time.
• the polishing rate of the silicon wafer using the polishing composition of Example 1 was 11 nm/min, and the polishing rate of the silicon wafer using the polishing composition of Example 8 was 9 nm/min.
• a silicon wafer polishing rate of 5 nm/min or more is practical.
• the polishing compositions of the examples can reduce the number of defects on the silicon wafer surface, and silicon wafers with good surface quality can be obtained.
• the polishing compositions of the comparative examples increase the number of defects, and the surface quality of the silicon wafers is inferior.
• the polishing composition according to this embodiment can improve the surface quality of the object to be polished after polishing.

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