WO2024161614A1 - 研磨液、研磨方法、部品の製造方法、及び、半導体部品の製造方法 - Google Patents
研磨液、研磨方法、部品の製造方法、及び、半導体部品の製造方法 Download PDFInfo
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- WO2024161614A1 WO2024161614A1 PCT/JP2023/003470 JP2023003470W WO2024161614A1 WO 2024161614 A1 WO2024161614 A1 WO 2024161614A1 JP 2023003470 W JP2023003470 W JP 2023003470W WO 2024161614 A1 WO2024161614 A1 WO 2024161614A1
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Classifications
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- H10P52/00—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
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- H10P95/062—
Definitions
- This disclosure relates to polishing fluids, polishing methods, component manufacturing methods, semiconductor component manufacturing methods, etc.
- CMP chemical mechanical polishing
- CVD chemical vapor deposition
- planarization by CMP is essential to ensure the depth of focus in lithography. If the surface of the polished member is uneven, it may cause inconveniences such as making it impossible to focus in the exposure process or not being able to sufficiently form a fine wiring structure.
- CMP is also applied to the process of forming element isolation (inter-element isolation; STI: shallow trench isolation) regions by polishing a plasma oxide film (BPSG, HDP-SiO 2 , p-TEOS, etc.) in the device manufacturing process; the process of forming an ILD film (an interlayer insulating film; an insulating film that electrically insulates metal members (wiring, etc.) in the same layer); and the process of planarizing a plug (e.g., an Al/Cu plug) after embedding a film containing silicon oxide in a metal wiring.
- ILD film an interlayer insulating film; an insulating film that electrically insulates metal members (wiring, etc.) in the same layer
- planarizing a plug e.g., an Al/Cu plug
- CMP is usually performed using a device capable of supplying a polishing liquid onto a polishing member (such as a polishing pad).
- the surface of the member to be polished is then polished by pressing the member to be polished against the polishing member while supplying a polishing liquid between the surface (front surface) of the member to be polished and the polishing member.
- the polishing liquid is one of the elemental technologies in CMP technology, and various polishing liquids have been developed to obtain high-performance polishing liquids (see, for example, Patent Document 1 below).
- One aspect of the present disclosure is to provide a polishing liquid capable of achieving an excellent polishing rate for USG. Another aspect of the present disclosure is to provide a polishing method using the polishing liquid. Another aspect of the present disclosure is to provide a method for manufacturing a component using a polished member polished by the polishing method. Another aspect of the present disclosure is to provide a method for manufacturing a semiconductor component using a polished member polished by the polishing method.
- a polishing liquid for polishing undoped silicate glass having a pH of 3.0 or more.
- the polishing liquid according to [1] having a pH of 3.5 to 8.0.
- the polishing liquid according to [1] or [2] which contains abrasive grains.
- the polishing liquid according to [3], wherein the abrasive grains contain a cerium-based compound.
- (A) The polishing liquid according to any one of [1] to [4], which contains polyglycerin.
- the polishing liquid according to [5], wherein the content of the component (A) is 0.001 to 10 mass %.
- [7] The polishing liquid according to any one of [1] to [6], containing (B) a compound having two or more nitrogen atoms to which a hydroxyalkyl group is bonded. [8] The polishing liquid according to [7], wherein the component (B) contains ethylenedinitrilotetrapropanol. [9] The polishing liquid according to [7] or [8], wherein the content of the component (B) is 0.001 to 5 mass %.
- a polishing method comprising a step of polishing a surface of a polishing member containing undoped silicate glass using the polishing liquid according to any one of [1] to [13].
- a method for manufacturing a part comprising obtaining a part using a polished member polished by the polishing method according to [14].
- a method for producing a semiconductor component comprising obtaining a semiconductor component using a polished member polished by the polishing method according to [14].
- a polishing liquid capable of achieving an excellent polishing rate for USG can be provided.
- a polishing method using the polishing liquid can be provided.
- a method for manufacturing a component using a polished member polished by the polishing method can be provided.
- a method for manufacturing a semiconductor component using a polished member polished by the polishing method can be provided.
- the numerical range indicated using “ ⁇ ” indicates a range including the numerical values described before and after “ ⁇ ” as the minimum and maximum values, respectively.
- the numerical range “A or more” means a range exceeding A and A.
- the numerical range “A or less” means a range less than A and A.
- the upper limit or lower limit of a numerical range of a certain stage can be arbitrarily combined with the upper limit or lower limit of a numerical range of another stage.
- the upper limit or lower limit of the numerical range may be replaced with a value shown in the example.
- “A or B” may include either A or B, or may include both.
- the materials exemplified in this specification may be used alone or in combination of two or more types.
- the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
- film includes a structure having a shape formed over the entire surface when observed in a plan view, as well as a structure having a shape formed only in a portion.
- process includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved. "Hydroxy group” does not include the OH structure contained in a carboxy group.
- the polishing liquid according to this embodiment is a polishing liquid for polishing USG (undoped silicate glass), and the pH of the polishing liquid is 3.0 or more.
- USG is silicon oxide without impurities added.
- USG can be formed by plasma CVD using silane (SiH 4 ) and oxygen (O 2 ) as raw materials.
- the polishing liquid according to this embodiment can be used as a polishing liquid for CMP.
- the polishing solution according to this embodiment can achieve an excellent polishing rate (high polishing rate) for USG.
- the silicon oxide film to be polished using the polishing liquid for example, a p-TEOS film formed by plasma CVD using tetraethoxysilane (TEOS) and oxygen (O 2 ) as raw materials may be used.
- TEOS tetraethoxysilane
- O 2 oxygen
- the polishing liquid according to this embodiment allows an excellent polishing rate for USG to be obtained.
- the polishing rate When polishing the surface of a workpiece using a polishing liquid, the polishing rate may be unstable for the outer periphery of the surface to be polished, which is about 2 mm from the outer periphery, due to reasons such as the tendency for the pressure applied during polishing to become unstable. Therefore, from the viewpoint of evaluating a stable polishing rate, the polishing rate of the inner region remaining after excluding the outer periphery of the surface to be polished may be evaluated. With the polishing liquid of this embodiment, it is possible to obtain an excellent polishing rate of USG in the inner region remaining after excluding the outer periphery of the surface to be polished.
- polishing liquid of this embodiment it is possible to obtain, in the evaluation method described in the examples below, a polishing rate of USG of, for example, 40 nm/min or more (preferably 50 nm/min or more, 100 nm/min or more, 300 nm/min or more, 500 nm/min or more, 700 nm/min or more, etc.) in the inner region remaining after excluding the outer periphery of the surface to be polished.
- a polishing rate of USG of, for example, 40 nm/min or more (preferably 50 nm/min or more, 100 nm/min or more, 300 nm/min or more, 500 nm/min or more, 700 nm/min or more, etc.) in the inner region remaining after excluding the outer periphery of the surface to be polished.
- the pH of the polishing liquid according to this embodiment is 3.0 or more from the viewpoint of obtaining an excellent polishing rate of USG.
- the pH may be more than 3.0, 3.1 or more, 3.2 or more, 3.3 or more, 3.4 or more, 3.5 or more, or 3.6 or more from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the pH may be 3.7 or more, 3.8 or more, 3.9 or more, 4.0 or more, 4.2 or more, 4.4 or more, 4.5 or more, or 4.6 or more.
- the pH may be 10.0 or less, less than 10.0, 9.5 or less, 9.0 or less, less than 9.0, 8.5 or less, 8.0 or less, less than 8.0, 7.5 or less, 7.0 or less, less than 7.0, 6.5 or less, 6.0 or less, less than 6.0, 5.5 or less, less than 5.5, 5.0 or less, less than 5.0, 4.6 or less, 4.5 or less, 4.4 or less, 4.2 or less, 4.0 or less, 3.9 or less, 3.8 or less, 3.7 or less, or 3.6 or less, from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the pH may be 3.5 or less, or 3.4 or less.
- the pH may be less than 5.0 from the viewpoint of easily suppressing the polishing rate of silicon nitride (SiN). From these viewpoints, the pH may be 3.0 to 10.0, 3.3 to 10.0, 3.5 to 10.0, 3.0 to 8.0, 3.3 to 8.0, 3.5 to 8.0, 3.0 to 7.0, 3.3 to 7.0, 3.5 to 7.0, 3.0 to 5.0, 3.3 to 5.0, or 3.5 to 5.0.
- the pH can be measured by the method described in the Examples.
- the polishing liquid according to the present embodiment may contain abrasive grains.
- the abrasive grains may contain a cerium-based compound (a compound containing cerium), alumina, silica, titania, zirconia, magnesia, mullite, silicon nitride, ⁇ -sialon, aluminum nitride, titanium nitride, silicon carbide, boron carbide, etc.
- the abrasive grains may contain a cerium-based compound from the viewpoint of easily obtaining an excellent polishing rate for USG.
- the abrasive grains may have a positive zeta potential (surface potential) in order to facilitate obtaining an excellent polishing rate for the USG.
- USG tends to have a negative zeta potential (surface potential) at a pH of 3.0 or higher, it is presumed that an excellent polishing rate is easily obtained with abrasive grains having a positive zeta potential, as the USG and the abrasive grains are attracted to each other by electrostatic attraction.
- the factors are not limited to the following.
- Abrasive grains containing a cerium-based compound can have a positive zeta potential.
- the zeta potential of the abrasive grains can be measured using a zeta potential measuring device (for example, a product name: DELSANANO C manufactured by Beckman Coulter, Inc.).
- Cerium compounds include cerium oxide (cerium oxide), cerium hydroxide (cerium hydroxide), ammonium cerium nitrate, cerium acetate, cerium sulfate hydrate, cerium bromate, cerium bromide, cerium chloride, cerium oxalate, cerium nitrate, cerium carbonate, etc.
- the abrasive grains may contain cerium oxide from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the content of the cerium-based compound in the abrasive grains may be 50 mass% or more, 70 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, 98 mass% or more, or 99 mass% or more based on the entire abrasive grains (all abrasive grains contained in the polishing liquid) from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the abrasive grains containing a cerium-based compound may be in an embodiment that is substantially composed of a cerium-based compound (an embodiment in which substantially 100 mass% of the abrasive grains are cerium-based compounds).
- the content of cerium oxide in the abrasive grains may be 50 mass% or more, 70 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, 98 mass% or more, or 99 mass% or more based on the entire abrasive grains (all abrasive grains contained in the polishing liquid) from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the abrasive grains containing cerium oxide may be in an embodiment in which the abrasive grains are substantially made of cerium oxide (an embodiment in which substantially 100 mass% of the abrasive grains are cerium oxide).
- the average particle size of the abrasive grains may be 50 nm or more, 70 nm or more, 100 nm or more, more than 100 nm, 105 nm or more, 110 nm or more, 115 nm or more, 120 nm or more, 125 nm or more, 130 nm or more, 135 nm or more, or 140 nm or more, from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the average particle size of the abrasive grains may be 500 nm or less, 300 nm or less, 200 nm or less, 180 nm or less, 150 nm or less, or 140 nm or less, from the viewpoint of easily suppressing the occurrence of polishing scratches.
- the average particle size of the abrasive grains may be 50 to 500 nm, 50 to 200 nm, 50 to 150 nm, 70 to 500 nm, 70 to 200 nm, 70 to 150 nm, 100 to 500 nm, 100 to 200 nm, or 100 to 150 nm.
- Average particle size of abrasive grains refers to the median value of the volume distribution measured by a laser diffraction/scattering particle size distribution measuring device for a sample of slurry in which the abrasive grains are dispersed, and can be measured using a device such as Microtrac MT3300EXII (trade name) manufactured by MicrotracBEL Corp.
- a sample can be prepared by dispersing the abrasive grains in water and adjusting the abrasive grain content so that the abrasive grain content is 0.25 mass% based on the total mass of the sample, and this sample can be set in the measuring device to measure the median value of the volume distribution.
- a sample When measuring the particle size of abrasive grains in a polishing liquid, a sample can be prepared by adjusting the abrasive grain content in the polishing liquid so that the abrasive grain content is 0.25 mass% based on the total mass of the sample, and this sample can be used for measurement in the same manner.
- the content of the abrasive grains may be in the following ranges based on the total mass of the polishing liquid, from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the content of the abrasive grains may be 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, 0.15 mass% or more, 0.2 mass% or more, 0.25 mass% or more, 0.3 mass% or more, 0.35 mass% or more, 0.4 mass% or more, 0.45 mass% or more, or 0.5 mass% or more.
- the content of the abrasive grains may be 10 mass% or less, 8 mass% or less, 5 mass% or less, 4 mass% or less, 3 mass% or less, 2.5 mass% or less, 2 mass% or less, 1.5 mass% or less, 1 mass% or less, 0.8 mass% or less, 0.6 mass% or less, or 0.5 mass% or less. From these perspectives, the content of the abrasive grains may be 0.01-10% by mass, 0.01-5% by mass, 0.01-2% by mass, 0.01-1% by mass, 0.05-10% by mass, 0.05-5% by mass, 0.05-2% by mass, 0.05-1% by mass, 0.1-10% by mass, 0.1-5% by mass, 0.1-2% by mass, or 0.1-1% by mass.
- the polishing liquid according to the present embodiment may contain water.
- the water is not particularly limited, but may contain at least one type of water selected from the group consisting of deionized water, ion-exchanged water, and ultrapure water.
- the polishing liquid according to the present embodiment may contain additives other than the abrasive grains and water.
- additives include the following components.
- the polishing liquid according to this embodiment may contain polyglycerin as the component (A) from the viewpoint of easily obtaining an excellent removal rate of USG.
- the weight average molecular weight of component (A) may be in the following ranges from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the weight average molecular weight of component (A) may be 350 or more, 400 or more, 450 or more, 500 or more, 550 or more, 600 or more, 650 or more, 700 or more, or 750 or more.
- the weight average molecular weight of component (A) may be 5000 or less, 4500 or less, 4000 or less, 3500 or less, 3000 or less, 2500 or less, 2400 or less, 2200 or less, 2000 or less, less than 2000, 1800 or less, 1600 or less, 1500 or less, 1400 or less, 1200 or less, 1000 or less, less than 1000, 950 or less, 900 or less, 850 or less, 800 or less, or 750 or less. From these perspectives, the weight average molecular weight of component (A) may be 350 to 5000, 350 to 3500, 350 to 1000, 500 to 5000, 500 to 3500, 500 to 1000, 700 to 5000, 700 to 3500, or 700 to 1000.
- the weight average molecular weight of the component (A) can be measured, for example, by gel permeation chromatography (GPC) under the following conditions.
- GPC gel permeation chromatography
- the hydroxyl value of the (A) component may be in the following range:
- the hydroxyl value of the (A) component may be 600 mgKOH/g or more, 650 mgKOH/g or more, 700 mgKOH/g or more, 750 mgKOH/g or more, 800 mgKOH/g or more, 830 mgKOH/g or more, 850 mgKOH/g or more, 870 mgKOH/g or more, 880 mgKOH/g or more, or 900 mgKOH/g or more.
- the hydroxyl value of component (A) may be 1500 mgKOH/g or less, 1200 mgKOH/g or less, 1000 mgKOH/g or less, 980 mgKOH/g or less, 960 mgKOH/g or less, 950 mgKOH/g or less, 930 mgKOH/g or less, 910 mgKOH/g or less, or 900 mgKOH/g or less.
- the hydroxyl value of the (A) component may be 600 to 1500 mgKOH/g, 600 to 1000 mgKOH/g, 600 to 950 mgKOH/g, 700 to 1500 mgKOH/g, 700 to 1000 mgKOH/g, 700 to 950 mgKOH/g, 800 to 1500 mgKOH/g, 800 to 1000 mgKOH/g, or 800 to 950 mgKOH/g.
- the hydroxyl value can be calculated from the following formula.
- the average degree of polymerization of glycerin in component (A) may be in the following ranges from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the average degree of polymerization may be 5 or more, 6 or more, 8 or more, or 10 or more.
- the average degree of polymerization may be 50 or less, 40 or less, 30 or less, 20 or less, 15 or less, 12 or less, or 10 or less. From these viewpoints, the average degree of polymerization may be 5 to 50, 5 to 40, 5 to 30, 8 to 20, 8 to 12, 10 to 30, or 5 to 10.
- the content of the (A) component may be in the following range based on the total mass of the polishing liquid.
- the content of the (A) component may be 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.03 mass% or more, 0.05 mass% or more, 0.08 mass% or more, 0.1 mass% or more, 0.12 mass% or more, 0.15 mass% or more, 0.18 mass% or more, or 0.2 mass% or more.
- the content of the (A) component may be 10 mass% or less, 8 mass% or less, 5 mass% or less, 3 mass% or less, 2 mass% or less, 1.5 mass% or less, 1 mass% or less, 0.8 mass% or less, 0.5 mass% or less, 0.45 mass% or less, 0.4 mass% or less, 0.35 mass% or less, 0.3 mass% or less, 0.25 mass% or less, or 0.2 mass% or less.
- the content of component (A) may be 0.001 to 10% by mass, 0.001 to 5% by mass, 0.001 to 1% by mass, 0.001 to 0.5% by mass, 0.01 to 10% by mass, 0.01 to 5% by mass, 0.01 to 1% by mass, 0.01 to 0.5% by mass, 0.05 to 10% by mass, 0.05 to 5% by mass, 0.05 to 1% by mass, 0.05 to 0.5% by mass, 0.1 to 10% by mass, 0.1 to 5% by mass, 0.1 to 1% by mass, or 0.1 to 0.5% by mass.
- the content of the (A) component may be in the following ranges per 100 parts by mass of the abrasive grains, from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the content of the (A) component may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more.
- the content of the (A) component may be 500 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, 150 parts by mass or less, 100 parts by mass or less, less than 100 parts by mass, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, or 40 parts by mass or less.
- the content of component (A) may be 1 to 500 parts by mass, 1 to 200 parts by mass, 1 to 50 parts by mass, 10 to 500 parts by mass, 10 to 200 parts by mass, 10 to 50 parts by mass, 30 to 500 parts by mass, 30 to 200 parts by mass, or 30 to 50 parts by mass.
- the polishing liquid according to this embodiment may contain, as component (B), a compound having two or more nitrogen atoms to which a hydroxyalkyl group is bonded (nitrogen-containing hydroxyalkyl compound) from the viewpoint of easily obtaining an excellent removal rate of USG.
- component (B) a hydroxyalkyl group is directly bonded to a nitrogen atom, and a hydroxy group is directly bonded to an alkyl group directly bonded to a nitrogen atom.
- an alkyl group having no substituent other than a hydroxy group can be used as the hydroxyalkyl group bonded to the nitrogen atom.
- the (B) component may contain a compound having a nitrogen atom bonded to two hydroxyalkyl groups, or may contain a compound having two or more nitrogen atoms bonded to two hydroxyalkyl groups, from the viewpoint of easily obtaining an excellent polishing rate for USG.
- the number of nitrogen atoms in one molecule of component (B) may be 2 to 5, 2 to 4, or 2 to 3, from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the number of hydroxyl groups in one molecule of component (B) may be 2 to 6, 2 to 5, 2 to 4, 3 to 6, 3 to 5, 3 to 4, 4 to 6, or 4 to 5, from the viewpoint of easily obtaining an excellent polishing rate of USG.
- component (B) may have a hydroxyalkyl group with 1 to 4, 2 to 4, 3 to 4, 1 to 3, 2 to 3, or 1 to 2 carbon atoms as the hydroxyalkyl group bonded to the nitrogen atom. From the viewpoint of easily obtaining an excellent polishing rate of USG, component (B) may have a hydroxyalkyl group with 1 to 3 or 1 to 2 hydroxy groups as the hydroxyalkyl group bonded to the nitrogen atom.
- the (B) component may have an alkylene group between the two nitrogen atoms to which the hydroxyalkyl group is bonded, from the viewpoint of easily obtaining an excellent polishing rate of the USG.
- the number of carbon atoms in such an alkylene group may be 1 to 4, 2 to 4, 1 to 3, 2 to 3, or 1 to 2, from the viewpoint of easily obtaining an excellent polishing rate of the USG.
- the (B) component may contain a compound represented by the following general formula (I) in order to facilitate obtaining an excellent polishing rate for USG.
- n is an integer of 1 or more
- R 11 , R 12 , R 13 and R 14 each independently represent a hydrogen atom or an organic group, one or both of R 11 and R 12 are hydroxyalkyl groups, and one or both of R 13 and R 14 are hydroxyalkyl groups.
- n may be within the range described above as the number of carbon atoms in the alkylene group between the two nitrogen atoms to which the hydroxyalkyl group is bonded.
- the organic group may be a substituted or unsubstituted alkyl group, a hydroxyalkyl group, or a group having a nitrogen atom to which a hydroxyalkyl group is bonded.
- substituent of the alkyl group include a hydroxy group, a carboxy group, an amino group, a sulfo group, and a nitro group.
- R 11 , R 12 , R 13 , or R 14 is a hydroxyalkyl group
- the number of carbon atoms in the hydroxyalkyl group may be within the range described above as the number of carbon atoms in the hydroxyalkyl group bonded to a nitrogen atom.
- component (B) examples include ethylene dinitrilotetraethanol (THEED: 2,2',2'',2'''-ethylene dinitrilotetraethanol (also known as N,N,N',N'-Tetrakis(2-hydroxyethyl)ethylenediamine), etc.), ethylene dinitrilotetrapropanol (EDTP: 1,1',1'',1'''-ethylene dinitrilotetra-2-propanol (also known as N,N,N',N'-Tetrakis(2-hydroxypropyl)ethylenediamine), etc.), and N,N,N',N'',N',N''-Pentakis(2-hydroxypropyl)diethylenetriamine.
- TEEED 2,2',2'',2'''-ethylene dinitrilotetraethanol
- EDTP 1,1',1'',1'''-ethylene dinitrilotetra-2-propanol
- the (B) component may contain at least one selected from the group consisting of ethylene dinitrilotetraethanol and ethylene dinitrilotetrapropanol, may contain ethylene dinitrilotetraethanol, or may contain ethylene dinitrilotetrapropanol. From the viewpoint of easily obtaining an excellent polishing rate of USG, the (B) component may contain a compound that does not have a carboxy group.
- the molecular weight of the (B) component may be in the following ranges from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the molecular weight of the (B) component may be 50 or more, 60 or more, 70 or more, 80 or more, 85 or more, 90 or more, 100 or more, 110 or more, 120 or more, 123 or more, 125 or more, 130 or more, 140 or more, 148 or more, 150 or more, 160 or more, 170 or more, 180 or more, 200 or more, 210 or more, 230 or more, 250 or more, more than 250, or 280 or more.
- the molecular weight of the (B) component may be 1000 or less, less than 1000, 900 or less, 800 or less, 700 or less, 600 or less, 500 or less, 400 or less, 350 or less, 300 or less, 280 or less, 250 or less, less than 250, or 240 or less. From these perspectives, the molecular weight of component (B) may be 50 to 1000, 50 to 500, 50 to 300, 50 to 250, 200 to 1000, 200 to 500, 200 to 300, 200 to 250, 250 to 1000, 250 to 500, or 250 to 300.
- the content B1 may be in the following range based on the total mass of the polishing liquid. From the viewpoint of easily obtaining an excellent polishing rate of USG, the content B1 may be 0.001 mass% or more, 0.003 mass% or more, 0.005 mass% or more, 0.008 mass% or more, or 0.01 mass% or more. The content B1 may be 0.012 mass% or more, 0.015 mass% or more, 0.018 mass% or more, or 0.02 mass% or more.
- the content B1 may be 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, 0.2 mass% or less, 0.15 mass% or less, 0.1 mass% or less, 0.08 mass% or less, 0.06 mass% or less, 0.05 mass% or less, 0.045 mass% or less, 0.04 mass% or less, 0.035 mass% or less, 0.03 mass% or less, 0.025 mass% or less, 0.02 mass% or less, 0.018 mass% or less, 0.015 mass% or less, 0.012 mass% or less, or 0.01 mass% or less.
- the content B1 may be 0.001 to 5 mass%, 0.001 to 1 mass%, 0.001 to 0.1 mass%, 0.001 to 0.015 mass%, 0.005 to 5 mass%, 0.005 to 1 mass%, 0.005 to 0.1 mass%, 0.005 to 0.015 mass%, 0.01 to 5 mass%, 0.01 to 1 mass%, 0.01 to 0.1 mass%, or 0.01 to 0.015 mass%.
- the content B2 may be in the following range per 100 parts by mass of abrasive grains. From the viewpoint of easily obtaining an excellent polishing rate of USG, the content B2 may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 1.5 parts by mass or more, or 2 parts by mass or more. The content B2 may be 2.5 parts by mass or more, 3 parts by mass or more, 3.5 parts by mass or more, or 4 parts by mass or more.
- the content B2 may be 100 parts by mass or less, less than 100 parts by mass, 80 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 6 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 3.5 parts by mass or less, 3 parts by mass or less, 2.5 parts by mass or less, or 2 parts by mass or less.
- the content B2 may be 0.1 to 100 parts by mass, 0.1 to 50 parts by mass, 0.1 to 10 parts by mass, 0.1 to 3 parts by mass, 0.5 to 100 parts by mass, 0.5 to 50 parts by mass, 0.5 to 10 parts by mass, 0.5 to 3 parts by mass, 1 to 100 parts by mass, 1 to 50 parts by mass, 1 to 10 parts by mass, or 1 to 3 parts by mass.
- the content B3 may be in the following range relative to 100 parts by mass of the (A) component. From the viewpoint of easily obtaining an excellent polishing rate of USG, the content B3 may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, or 5 parts by mass or more.
- the content B3 may be 6 parts by mass or more, 7 parts by mass or more, 8 parts by mass or more, 9 parts by mass or more, or 10 parts by mass or more.
- the content B3 may be 200 parts by mass or less, 150 parts by mass or less, 100 parts by mass or less, less than 100 parts by mass, 80 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 45 parts by mass or less, 40 parts by mass or less, 35 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 9 parts by mass or less, 8 parts by mass or less, 7 parts by mass or less, 6 parts by mass or less, or 5 parts by mass or less.
- the content B3 may be 0.1 to 200 parts by mass, 0.1 to 50 parts by mass, 0.1 to 30 parts by mass, 0.1 to 8 parts by mass, 1 to 200 parts by mass, 1 to 50 parts by mass, 1 to 30 parts by mass, 1 to 8 parts by mass, 5 to 200 parts by mass, 5 to 50 parts by mass, 5 to 30 parts by mass, or 5 to 8 parts by mass.
- the polishing liquid according to this embodiment may contain a 4-pyrone compound represented by the following general formula (1) (hereinafter, sometimes simply referred to as a "4-pyrone compound”), from the viewpoint of easily obtaining an excellent removal rate of USG.
- a 4-pyrone compound represented by the following general formula (1) hereinafter, sometimes simply referred to as a "4-pyrone compound”
- X 11 , X 12 and X 13 each independently represent a hydrogen atom or a monovalent substituent.
- 4-pyrone compounds are compounds that have a structure in which a hydroxy group is bonded to the carbon atom adjacent to the carbonyl group.
- “4-pyrone compounds” are heterocyclic compounds that have an oxy group and a carbonyl group, and a ⁇ -pyrone ring (six-membered ring) in which the carbonyl group is located at the 4th position relative to the oxy group.
- a hydroxy group is bonded to the carbon atom adjacent to the carboxy group in this ⁇ -pyrone ring, and the other carbon atoms may be substituted with substituents other than hydrogen atoms.
- X 11 , X 12 and X 13 are each independently a hydrogen atom or a monovalent substituent.
- the monovalent substituent include an aldehyde group, a hydroxy group, a carboxy group, a carboxylate group, a sulfonic acid group, a phosphoric acid group, a bromine atom, a chlorine atom, an iodine atom, a fluorine atom, a nitro group, a hydrazine group, an alkyl group (e.g., an alkyl group having 1 to 8 carbon atoms), an aryl group (e.g., an aryl group having 6 to 12 carbon atoms), an alkenyl group (e.g., an alkenyl group having 1 to 8 carbon atoms), and the like.
- the alkyl group, the aryl group, and the alkenyl group may be substituted with OH, COOH, Br, Cl, I, NO 2 , or the like.
- the substituent may be bonded to a carbon atom adjacent to the oxy group, that is, X 11 and X 12 may be a substituent. At least two of X 11 , X 12 and X 13 may be a hydrogen atom.
- the 4-pyrone compound may contain at least one selected from the group consisting of 3-hydroxy-2-methyl-4-pyrone (also known as 3-hydroxy-2-methyl-4H-pyran-4-one, maltol), 5-hydroxy-2-(hydroxymethyl)-4-pyrone (also known as 5-hydroxy-2-(hydroxymethyl)-4H-pyran-4-one, kojic acid), and 2-ethyl-3-hydroxy-4-pyrone (also known as 2-ethyl-3-hydroxy-4H-pyran-4-one), from the viewpoint of easily obtaining an excellent removal rate of USG, and may contain 3-hydroxy-2-methyl-4-pyrone.
- 3-hydroxy-2-methyl-4-pyrone also known as 3-hydroxy-2-methyl-4H-pyran-4-one, maltol
- 5-hydroxy-2-(hydroxymethyl)-4-pyrone also known as 5-hydroxy-2-(hydroxymethyl)-4H-pyran-4-one, kojic acid
- 2-ethyl-3-hydroxy-4-pyrone also known as 2-ethyl-3-hydroxy-4H-pyran-4-one
- the content of the 4-pyrone compound may be in the following range based on the total mass of the polishing liquid.
- the content of the 4-pyrone compound may be 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.015 mass% or more, 0.02 mass% or more, 0.025 mass% or more, 0.03 mass% or more, or 0.034 mass% or more.
- the content of the 4-pyrone compound may be 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.8 mass% or less, 0.5 mass% or less, 0.3 mass% or less, 0.2 mass% or less, 0.15 mass% or less, 0.1 mass% or less, 0.08 mass% or less, 0.05 mass% or less, 0.04 mass% or less, or 0.035 mass% or less. From these viewpoints, the content of the 4-pyrone compound may be 0.001 to 5% by mass, 0.001 to 1% by mass, 0.001 to 0.1% by mass, 0.01 to 5% by mass, 0.01 to 1% by mass, 0.01 to 0.1% by mass, 0.03 to 5% by mass, 0.03 to 1% by mass, or 0.03 to 0.1% by mass.
- the content of the 4-pyrone compound may be in the following ranges per 100 parts by mass of abrasive grains, from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the content of the 4-pyrone compound may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, or 6 parts by mass or more.
- the content of the 4-pyrone compound may be 100 parts by mass or less, less than 100 parts by mass, 80 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, or 8 parts by mass or less. From these viewpoints, the content of the 4-pyrone compound may be 0.1 to 100 parts by mass, 0.1 to 50 parts by mass, 0.1 to 10 parts by mass, 1 to 100 parts by mass, 1 to 50 parts by mass, 1 to 10 parts by mass, 5 to 100 parts by mass, 5 to 50 parts by mass, or 5 to 10 parts by mass.
- the content of the 4-pyrone compound may be in the following ranges per 100 parts by mass of component (A).
- the content of the 4-pyrone compound may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 8 parts by mass or more, 10 parts by mass or more, 12 parts by mass or more, or 15 parts by mass or more.
- the content of the 4-pyrone compound may be 100 parts by mass or less, less than 100 parts by mass, 80 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, or 18 parts by mass or less. From these viewpoints, the content of the 4-pyrone compound may be 0.1 to 100 parts by mass, 0.1 to 50 parts by mass, 0.1 to 20 parts by mass, 1 to 100 parts by mass, 1 to 50 parts by mass, 1 to 20 parts by mass, 10 to 100 parts by mass, 10 to 50 parts by mass, or 10 to 20 parts by mass.
- the content of the 4-pyrone compound may be in the following ranges relative to 100 parts by mass of component (B). From the viewpoint of easily obtaining an excellent polishing rate of USG, the content of the 4-pyrone compound may be 10 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, 80 parts by mass or more, 100 parts by mass or more, more than 100 parts by mass, 120 parts by mass or more, 150 parts by mass or more, 180 parts by mass or more, 200 parts by mass or more, 250 parts by mass or more, or 300 parts by mass or more.
- the content of the 4-pyrone compound may be 1000 parts by mass or less, 800 parts by mass or less, 600 parts by mass or less, 500 parts by mass or less, 400 parts by mass or less, or 350 parts by mass or less.
- the content of the 4-pyrone compound may be 300 parts by mass or less, 250 parts by mass or less, 200 parts by mass or less, or 180 parts by mass or less.
- the content of the 4-pyrone compound may be 10 to 1000 parts by mass, 10 to 500 parts by mass, 10 to 200 parts by mass, 50 to 1000 parts by mass, 50 to 500 parts by mass, 50 to 200 parts by mass, 100 to 1000 parts by mass, 100 to 500 parts by mass, 100 to 200 parts by mass, 200 to 1000 parts by mass, or 200 to 500 parts by mass.
- the polishing liquid according to the present embodiment may contain an acid component.
- the acid component include organic acid components such as organic acids and organic acid salts; inorganic acid components such as inorganic acids and inorganic acid salts.
- the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, and boric acid.
- the organic acid salt or inorganic acid salt include alkali metal salts (sodium salts, potassium salts, and the like), ammonium salts, and the like.
- the acid component may contain, as an organic acid component, at least one carboxylic acid component selected from the group consisting of carboxylic acids and carboxylates, and may contain at least one saturated monocarboxylic acid component selected from the group consisting of saturated monocarboxylic acids and saturated monocarboxylates.
- the acid component contains a carboxylic acid component
- a pH of 3.0 or higher makes it easier for cations (hydrogen ions, metal ions, etc.) to dissociate in the carboxyl groups or carboxylate bases of at least a portion of the carboxylic acid component, and the carboxylic acid component from which the cations have dissociated is more likely to act favorably on USG.
- the carboxylic acid component from which the cations have not dissociated is less likely to adhere to USG, and is less likely to inhibit polishing of USG. It is presumed that these actions make it easier to obtain an excellent polishing rate for USG. However, the factors that make it easier to obtain an excellent polishing rate are not limited to the above.
- Saturated monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hydroangelic acid, caproic acid, 2-methylpentanoic acid, 4-methylpentanoic acid, 2,3-dimethylbutanoic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, and 3,3-dimethylbutanoic acid.
- the saturated monocarboxylic acid may include an aliphatic carboxylic acid from the viewpoint of easily obtaining an excellent polishing rate of USG.
- the saturated monocarboxylic acid may include a saturated monocarboxylic acid having 2 to 6 carbon atoms from the viewpoint of easily obtaining an excellent polishing rate of USG, and may include at least one selected from the group consisting of acetic acid and propionic acid.
- the content of the acid component or the content of the saturated monocarboxylic acid may be in the following ranges based on the total mass of the polishing liquid.
- the content of the acid component or the content of the saturated monocarboxylic acid may be 0.001 mass% or more, 0.005 mass% or more, 0.01 mass% or more, 0.03 mass% or more, 0.05 mass% or more, 0.08 mass% or more, or 0.09 mass% or more.
- the content of the acid component or the content of the saturated monocarboxylic acid may be 5 mass% or less, 3 mass% or less, 1 mass% or less, 0.8 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, 0.2 mass% or less, or 0.1 mass% or less.
- the content of the acid component or the content of the saturated monocarboxylic acid may be 0.001 to 5% by mass, 0.001 to 1% by mass, 0.001 to 0.5% by mass, 0.01 to 5% by mass, 0.01 to 1% by mass, 0.01 to 0.5% by mass, 0.05 to 5% by mass, 0.05 to 1% by mass, or 0.05 to 0.5% by mass.
- the polishing liquid according to the present embodiment may contain other additives (additives other than those mentioned above) according to the desired properties.
- additives include nonionic polymers, cationic compounds, pH adjusters, polar solvents such as ethanol and acetone, and cyclic monocarboxylic acids.
- a pH adjuster can be used to adjust the pH to the above range.
- bases such as sodium hydroxide, ammonia (e.g., ammonia water), potassium hydroxide, and calcium hydroxide.
- the above-mentioned acid components may also be used to adjust the pH.
- the polishing liquid may be prepared without using a pH adjuster, and this polishing liquid may be used directly for polishing.
- the polishing liquid according to this embodiment may contain a compound a having a molecular weight of 100,000 or less and 4 or more hydroxyl groups, or may not contain compound a.
- the polishing liquid according to this embodiment may contain a compound b having 4 or more amino groups, or may not contain compound b.
- the content of compound b may be 0.001 mass% or less, less than 0.001 mass%, 0.0001 mass% or less, 0.00001 mass% or less, or substantially 0 mass%, based on the total mass of the polishing liquid.
- the mass ratio of the content of compound a to the content of compound b (compound a/compound b) may be 0.10 or less, or less than 0.10.
- the polishing liquid according to this embodiment can be classified into (a) a normal type, (b) a concentrated type, and (c) a multi-liquid type (e.g., a two-liquid type, a polishing liquid set), and the like, and the preparation method and the method of use differ depending on the type.
- the normal type is a polishing liquid that can be used as is without pretreatment such as dilution during polishing.
- the normal type can be obtained, for example, by dispersing or dissolving abrasive grains and additives in water.
- the concentrated type is a polishing liquid in which the components are concentrated compared to the normal type (a) for convenience in storage and transportation.
- the concentrated type is diluted with water immediately before use so that the components reach the desired content.
- the multiple liquid type is a polishing liquid in which the components are separated into multiple liquids (for example, a first liquid containing one component and a second liquid containing another component) during storage or transportation, and these liquids are mixed when used.
- the components contained in each liquid are optional.
- the multiple liquid type is, for example, a polishing liquid set for obtaining a polishing liquid by mixing a first liquid (slurry) and a second liquid (additive liquid).
- a polishing liquid set for obtaining a polishing liquid by mixing a first liquid (slurry) and a second liquid (additive liquid).
- the components of the polishing liquid are stored separately as a first liquid and a second liquid, the first liquid contains abrasive grains and water, and the second liquid contains at least one type of additive and water.
- the first liquid may contain at least one type of additive.
- the components of the polishing liquid may be separated into three or more liquids.
- a multi-liquid type polishing liquid is useful when the components are combined in a way that, when mixed, the polishing properties tend to decrease in a relatively short time due to the aggregation of abrasive grains, etc.
- at least one of the liquids may be a concentrated type. In this case, when using the polishing liquid, each liquid can be mixed with water.
- the polishing method according to the present embodiment includes a polishing step of polishing the surface of a polished member containing USG using the polishing liquid according to the present embodiment.
- the polishing liquid used in the polishing step may be a polishing liquid obtained by mixing a plurality of liquids (e.g., the first liquid and the second liquid) in the above-mentioned polishing liquid set. That is, the polishing method according to the present embodiment may include a polishing step of polishing the surface of a polished member containing USG using the polishing liquid obtained by mixing a plurality of liquids (e.g., the first liquid and the second liquid) in the above-mentioned polishing liquid set.
- the polishing process may be a process in which the polishing liquid according to this embodiment is supplied between a member to be polished and a polishing member (a member for polishing, such as a polishing pad), and the polishing surface of the member to be polished is polished by the polishing member.
- the polishing process may be a process in which the inner region remaining on the polishing surface of the member to be polished that contains USG is polished, excluding the outer periphery.
- the component manufacturing method according to the present embodiment includes a component manufacturing step of obtaining a component using a polished member polished by the polishing method according to the present embodiment.
- the component according to the present embodiment is a component obtained by the component manufacturing method according to the present embodiment.
- the component according to the present embodiment is not particularly limited, and may be an electronic component (e.g., a semiconductor component such as a semiconductor package), a wafer (e.g., a semiconductor wafer), or a chip (e.g., a semiconductor chip).
- an electronic component is obtained using a polished member polished by the polishing method according to the present embodiment.
- a semiconductor component e.g., a semiconductor package
- the component manufacturing method according to the present embodiment may include a polishing step of polishing a polished member by the polishing method according to the present embodiment before the component manufacturing step.
- the component manufacturing method according to the present embodiment may include, as one aspect of the component manufacturing process, a singulation process for singulating the polished member polished by the polishing method according to the present embodiment.
- the singulation process may be, for example, a process for dicing a wafer (e.g., a semiconductor wafer) polished by the polishing method according to the present embodiment to obtain chips (e.g., semiconductor chips).
- the electronic component manufacturing method according to the present embodiment may include a process for singulating the polished member polished by the polishing method according to the present embodiment to obtain electronic components (e.g., semiconductor components).
- the semiconductor component manufacturing method according to the present embodiment may include a process for singulating the polished member polished by the polishing method according to the present embodiment to obtain semiconductor components (e.g., semiconductor packages).
- the manufacturing method of the component according to the present embodiment may include, as one aspect of the component manufacturing process, a connection process for connecting (e.g., electrically connecting) the polished member polished by the polishing method according to the present embodiment to another connected object.
- the connected object to be connected to the polished member polished by the polishing method according to the present embodiment is not particularly limited, and may be the polished member polished by the polishing method according to the present embodiment, or may be a connected object different from the polished member polished by the polishing method according to the present embodiment.
- the polished member and the connected object may be directly connected (connected in a state where the polished member and the connected object are in contact with each other), or the polished member and the connected object may be connected via another member (such as a conductive member).
- the connection process may be performed before the singulation process, after the singulation process, or before or after the singulation process.
- the connecting step may be a step of connecting the polished surface of the polished member polished by the polishing method according to this embodiment to the connected body, or may be a step of connecting the connecting surface of the polished member polished by the polishing method according to this embodiment to the connecting surface of the connected body.
- the connecting surface of the polished member may be the polished surface polished by the polishing method according to this embodiment.
- the connecting step can obtain a connected body including the polished member and the connected body.
- the connecting step if the connecting surface of the polished member has a metal part, the connected body may be brought into contact with the metal part.
- the connecting step if the connecting surface of the polished member has a metal part and the connecting surface of the connected body has a metal part, the metal parts may be brought into contact with each other.
- the metal part may contain, for example, copper.
- the device according to this embodiment (e.g., an electronic device such as a semiconductor device) comprises a polished member polished by the polishing method according to this embodiment, and at least one selected from the group consisting of the parts according to this embodiment.
- ⁇ Experiment A Examples and Comparative Examples ⁇ ⁇ Preparation of cerium oxide powder> 40 kg of cerium carbonate hydrate was divided and placed in 10 alumina containers, and each was calcined in air at 830°C for 2 hours to obtain a total of 20 kg of yellowish white powder. Phase identification of this powder was performed using X-ray diffraction, and it was confirmed that the powder contained polycrystalline cerium oxide. The particle size of the powder obtained by calcination was observed using a SEM and was in the range of 20 to 100 ⁇ m. Next, 20 kg of the cerium oxide powder was dry-pulverized using a jet mill to obtain cerium oxide powder. The specific surface area of the cerium oxide powder after pulverization was 9.4 m 2 /g. The specific surface area was measured by the BET method.
- the cerium oxide mixture that had been delivered after ultrasonic irradiation was placed in four 1,000 mL polyethylene containers, each containing 800 g ⁇ 8 g.
- the cerium oxide mixture in each container was centrifuged for 20 minutes under conditions that resulted in a centrifugal force of 500 G on the periphery. After centrifugation, the supernatant fraction was collected from the container to obtain a slurry.
- the slurry contained approximately 10.0% by mass of cerium oxide particles (abrasive grains) based on the total mass.
- a sample for particle size measurement was obtained by diluting the slurry with pure water so that the abrasive content (based on the total mass of the sample) was 0.25% by mass.
- the average particle size of the abrasive particles in this sample was measured using a laser diffraction/scattering particle size distribution measuring device (Microtrac MT3300EXII, manufactured by MicrotracBEL Corp.), and the average particle size was found to be 140 nm.
- a polishing liquid (polishing liquid for CMP) was obtained by mixing the above-mentioned slurry, polyglycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name Polyglycerin #750, decamer, weight average molecular weight 750, hydroxyl value 900 mgKOH/g), EDTP (1,1',1'',1'''-ethylenedinitrilotetra-2-propanol), maltol, an acid component, and deionized water.
- the pH of the polishing liquid was adjusted by adjusting the contents of propionic acid and acetic acid as acid components.
- the content of the abrasive grains was 0.5 mass%
- the content of polyglycerin was 0.2 mass%
- the content of EDTP was as shown in Table 1 (0.01 mass% or 0.02 mass%)
- the content of maltol was 0.034 mass%
- the contents of propionic acid and acetic acid were as shown in Table 1.
- the above-mentioned evaluation wafer was polished using a polishing machine (manufactured by Ebara Corporation, product name: F-REX300X). The above-mentioned evaluation wafer was set on a holder having an adsorption pad. A polishing pad made of porous urethane resin (manufactured by DuPont, product name: IK4250H) was attached to a polishing platen having a diameter of 700 mm.
- the holder was placed on the polishing pad with the surface of the evaluation wafer facing down.
- the retainer ring pressure and membrane pressure were set to 34 kPa and 21 kPa, respectively.
- the polishing pad attached to the polishing platen was dropped with the above-mentioned polishing liquid at a flow rate of 250 mL/min, while the polishing platen and the evaluation wafer were rotated at 93 min -1 and 87 min -1 , respectively, to polish the surface to be polished.
- the polishing time was 20 seconds.
- the evaluation wafer after polishing was thoroughly washed with pure water using a polyvinyl alcohol brush and then dried.
- Example 2 Reference Example ⁇ Except for using a wafer with no pattern and a diameter of 300 mm (shape: circular) having a p-TEOS film (initial film thickness: 2000 nm) on its surface as the blanket wafer, the polishing rate was evaluated in the same manner as in Comparative Example 1. The polishing rate when the polishing liquid of Comparative Example 1 was used was 397 nm/min.
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Abstract
Description
[1]pHが3.0以上である、Undoped Silicate Glass研磨用の研磨液。
[2]pHが3.5~8.0である、[1]に記載の研磨液。
[3]砥粒を含有する、[1]又は[2]に記載の研磨液。
[4]前記砥粒がセリウム系化合物を含む、[3]に記載の研磨液。
[5](A)ポリグリセリンを含有する、[1]~[4]のいずれか一つに記載の研磨液。
[6]前記(A)成分の含有量が0.001~10質量%である、[5]に記載の研磨液。
[7](B)ヒドロキシアルキル基が結合した2以上の窒素原子を有する化合物を含有する、[1]~[6]のいずれか一つに記載の研磨液。
[8]前記(B)成分がエチレンジニトリロテトラプロパノールを含む、[7]に記載の研磨液。
[9]前記(B)成分の含有量が0.001~5質量%である、[7]又は[8]に記載の研磨液。
[10]下記一般式(1)で表される4-ピロン系化合物を含有する、[1]~[9]のいずれか一つに記載の研磨液。
[11]前記4-ピロン系化合物が、3-ヒドロキシ-2-メチル-4-ピロン、5-ヒドロキシ-2-(ヒドロキシメチル)-4-ピロン、及び、2-エチル-3-ヒドロキシ-4-ピロンからなる群より選ばれる少なくとも一種を含む、[10]に記載の研磨液。
[12]前記4-ピロン系化合物の含有量が0.001~5質量%である、[10]又は[11]に記載の研磨液。
[13]飽和モノカルボン酸を含有する、[1]~[12]のいずれか一つに記載の研磨液。
[14][1]~[13]のいずれか一つに記載の研磨液を用いて、Undoped Silicate Glassを含有する被研磨部材の被研磨面を研磨する工程を備える、研磨方法。
[15][14]に記載の研磨方法により研磨された被研磨部材を用いて部品を得る、部品の製造方法。
[16][14]に記載の研磨方法により研磨された被研磨部材を用いて半導体部品を得る、半導体部品の製造方法。
本実施形態に係る研磨液は、USG(Undoped Silicate Glass)研磨用の研磨液であり、当該研磨液のpHは、3.0以上である。USGは、不純物が添加された酸化ケイ素(例えば、フッ素を含有するFSG)とは異なり、不純物が添加されていない酸化ケイ素である。USGは、例えば、原料としてシラン(SiH4)及び酸素(O2)を用いてプラズマCVDにより形成することができる。本実施形態に係る研磨液は、CMP用研磨液として用いることができる。
本実施形態に係る研磨液のpHは、USGの優れた研磨速度を得る観点から、3.0以上である。pHは、USGの優れた研磨速度を得やすい観点から、3.0超、3.1以上、3.2以上、3.3以上、3.4以上、3.5以上、又は、3.6以上であってよい。pHは、3.7以上、3.8以上、3.9以上、4.0以上、4.2以上、4.4以上、4.5以上、又は、4.6以上であってよい。pHは、USGの優れた研磨速度を得やすい観点から、10.0以下、10.0未満、9.5以下、9.0以下、9.0未満、8.5以下、8.0以下、8.0未満、7.5以下、7.0以下、7.0未満、6.5以下、6.0以下、6.0未満、5.5以下、5.5未満、5.0以下、5.0未満、4.6以下、4.5以下、4.4以下、4.2以下、4.0以下、3.9以下、3.8以下、3.7以下、又は、3.6以下であってよい。pHは、3.5以下、又は、3.4以下であってよい。pHが7.0未満である場合、砥粒は正のゼータ電位(表面電位)を有しやすい。pHは、窒化ケイ素(SiN)の研磨速度を抑制しやすい観点から、5.0未満であってよい。これらの観点から、pHは、3.0~10.0、3.3~10.0、3.5~10.0、3.0~8.0、3.3~8.0、3.5~8.0、3.0~7.0、3.3~7.0、3.5~7.0、3.0~5.0、3.3~5.0、又は、3.5~5.0であってよい。pHは、実施例に記載の方法により測定できる。
本実施形態に係る研磨液は、砥粒を含有してよい。砥粒は、セリウム系化合物(セリウムを含む化合物)、アルミナ、シリカ、チタニア、ジルコニア、マグネシア、ムライト、窒化ケイ素、α-サイアロン、窒化アルミニウム、窒化チタン、炭化ケイ素、炭化ホウ素等を含むことができる。砥粒は、USGの優れた研磨速度を得やすい観点から、セリウム系化合物を含んでよい。
本実施形態に係る研磨液は、水を含有することができる。水は、特に制限されるものではないが、脱イオン水、イオン交換水及び超純水からなる群より選ばれる少なくとも一種を含んでよい。
本実施形態に係る研磨液は、砥粒及び水以外の成分として添加剤を含有することができる。添加剤としては、以下の成分等が挙げられる。
本実施形態に係る研磨液は、USGの優れた研磨速度を得やすい観点から、(A)成分として、ポリグリセリンを含有してよい。
[条件]
試料:20μL
標準ポリエチレングリコール:ポリマー・ラボラトリー社製、標準ポリエチレングリコール(分子量:106、194、440、600、1470、4100、7100、10300、12600及び23000)
検出器:昭和電工株式会社製、RI-モニター、商品名「Syodex-RI SE-61」
ポンプ:株式会社日立製作所製、商品名「L-6000」
カラム:昭和電工株式会社製の商品名「GS-220HQ」及び「GS-620HQ」をこの順番で連結して使用
溶離液:0.4mol/Lの塩化ナトリウム水溶液
測定温度:30℃
流速:1.00mL/min
測定時間:45min
水酸基価=56110×(重合度+2)/(74×重合度+18)
本実施形態に係る研磨液は、USGの優れた研磨速度を得やすい観点から、(B)成分として、ヒドロキシアルキル基が結合した2以上の窒素原子を有する化合物(窒素含有ヒドロキシアルキル化合物)を含有してよい。(B)成分では、窒素原子にヒドロキシアルキル基が直接結合しており、窒素原子に直接結合したアルキル基にヒドロキシ基が直接結合している。(B)成分は、窒素原子に結合したヒドロキシアルキル基として、ヒドロキシ基以外の置換基を有しないアルキル基を用いることができる。
本実施形態に係る研磨液は、USGの優れた研磨速度を得やすい観点から、下記一般式(1)で表される4-ピロン系化合物(以下、場合により、単に「4-ピロン系化合物」という)を含有してよい。
本実施形態に係る研磨液は、酸成分を含有してよい。酸成分としては、有機酸、有機酸塩等の有機酸成分;無機酸、無機酸塩等の無機酸成分などが挙げられる。無機酸としては、硝酸、硫酸、塩酸、リン酸、ホウ酸等が挙げられる。有機酸塩又は無機酸塩としては、アルカリ金属塩(ナトリウム塩、カリウム塩等)、アンモニウム塩などが挙げられる。
本実施形態に係る研磨液は、所望とする特性に合わせて他の添加剤(上述の各添加剤に該当しない添加剤)を含有してよい。このような添加剤としては、非イオン性ポリマ;カチオン性化合物;pH調整剤;エタノール、アセトン等の極性溶媒;環状モノカルボン酸などが挙げられる。
本実施形態に係る研磨液は、(a)通常タイプ、(b)濃縮タイプ、(c)複数液タイプ(例えば2液タイプ。研磨液セット)等に分類でき、タイプによってそれぞれ調製法及び使用法が相違する。
本実施形態に係る研磨方法は、本実施形態に係る研磨液を用いて、USGを含有する被研磨部材の被研磨面を研磨する研磨工程を含む。研磨工程で用いられる研磨液は、上述の研磨液セットにおける複数の液(例えば、第1の液及び第2の液)を混合して得られる研磨液であってもよい。すなわち、本実施形態に係る研磨方法は、上述の研磨液セットにおける複数の液(例えば、第1の液及び第2の液)を混合して得られる研磨液を用いて、USGを含有する被研磨部材の被研磨面を研磨する研磨工程を含んでよい。
本実施形態に係る部品の製造方法は、本実施形態に係る研磨方法により研磨された被研磨部材を用いて部品を得る部品作製工程を備える。本実施形態に係る部品は、本実施形態に係る部品の製造方法により得られる部品である。本実施形態に係る部品は、特に限定されず、電子部品(例えば、半導体パッケージ等の半導体部品)であってよく、ウエハ(例えば半導体ウエハ)であってよく、チップ(例えば半導体チップ)であってよい。本実施形態に係る部品の製造方法の一態様として、本実施形態に係る電子部品の製造方法では、本実施形態に係る研磨方法により研磨された被研磨部材を用いて電子部品を得る。本実施形態に係る部品の製造方法の一態様として、本実施形態に係る半導体部品の製造方法では、本実施形態に係る研磨方法により研磨された被研磨部材を用いて半導体部品(例えば半導体パッケージ)を得る。本実施形態に係る部品の製造方法は、部品作製工程の前に、本実施形態に係る研磨方法により被研磨部材を研磨する研磨工程を備えてよい。
<酸化セリウム粉末の作製>
炭酸セリウム水和物40kgをアルミナ製容器10個に分けて入れ、それぞれ830℃で2時間、空気中で焼成して黄白色の粉末を計20kg得た。この粉末についてX線回折法で相同定を行い、当該粉末が多結晶体の酸化セリウムを含むことを確認した。焼成によって得られた粉末の粒径をSEMで観察したところ、20~100μmの範囲であった。次いで、ジェットミルを用いて酸化セリウム粉末20kgの乾式粉砕を行うことにより酸化セリウム粉末を得た。粉砕後の酸化セリウム粉末の比表面積は9.4m2/gであった。比表面積の測定はBET法によって実施した。
上記で得られた酸化セリウム粉末15.0kg及び脱イオン水84.5kgを容器内に入れて混合した。次に、酢酸を0.03kg添加した後、10分間撹拌することにより酸化セリウム混合液を得た。この酸化セリウム混合液を別の容器に30分かけて送液した。その間、送液する配管内で、酸化セリウム混合液に対して超音波周波数400kHzにて超音波照射を行った。
上述のスラリ、ポリグリセリン(阪本薬品工業株式会社製、商品名ポリグリセリン#750、10量体、重量平均分子量750、水酸基価900mgKOH/g)、EDTP(1,1’,1’’,1’’’-エチレンジニトリロテトラ-2-プロパノール)、マルトール、酸成分及び脱イオン水を混合することにより研磨液(CMP用研磨液)を得た。酸成分としてプロピオン酸及び酢酸の含有量を調整することにより研磨液のpHを調整した。研磨液の全量を基準として、砥粒の含有量は0.5質量%であり、ポリグリセリンの含有量は0.2質量%であり、EDTPの含有量は表1に示すとおり(0.01質量%又は0.02質量%)であり、マルトールの含有量は0.034質量%であり、プロピオン酸及び酢酸の含有量は表1に示すとおりであった。
(研磨液のpH)
下記の条件で研磨液のpHを測定した。結果を表1に示す。
測定温度:25℃
測定装置:株式会社堀場製作所の商品名:Model(D-71)
測定方法:フタル酸塩pH標準液(pH:4.01)と、中性リン酸塩pH標準液(pH:6.86)と、ホウ酸塩pH標準液(pH:9.18)とをpH標準液として用いてpHメーターを3点校正した後、pHメーターの電極を研磨液に入れて、2min以上経過して安定した後のpHを前記測定装置により測定した。
(評価用ウエハの準備)
ブランケットウエハとして、表面にUSG膜(初期膜厚:2000nm)を有する直径300mm(形状:円形)のパターン無しのウエハを準備した。
研磨装置(株式会社荏原製作所製、商品名:F-REX300X)を用いて上述の評価用ウエハを研磨した。吸着パッドを有するホルダーに上述の評価用ウエハをセットした。直径700mmの研磨定盤に多孔質ウレタン樹脂製の研磨パッド(DuPоnt社製、商品名:IK4250H)を貼り付けた。
光干渉式膜厚測定装置(Nоva Ltd.製、商品名:nоva i500)を用いて、USG膜において外周から2mmの外周部を除外して残る内側領域における複数の測定点の膜厚変化量を測定し、各測定点の研磨速度を得た。測定点は、内側領域の中心点を通る直径方向において、中心点から-148mm、-147mm、-145mm、-140mm、-135mm、・・・(5mm間隔)・・・、-10mm及び-5mmの箇所、中心点、並びに、中心点から+5mm、+10mm、・・・(5mm間隔)・・・、+135mm、+140mm、+145mm、+147mm及び+148mmの箇所であった。これらの測定点における研磨速度の平均値(USG研磨速度)を表1に示す。
ブランケットウエハとして、表面にp-TEOS膜(初期膜厚:2000nm)を有する直径300mm(形状:円形)のパターン無しのウエハを用いたこと以外は比較例1と同様に研磨速度の評価を行った。比較例1の研磨液を用いた場合における研磨速度は397nm/minであった。
Claims (16)
- pHが3.0以上である、Undoped Silicate Glass研磨用の研磨液。
- pHが3.5~8.0である、請求項1に記載の研磨液。
- 砥粒を含有する、請求項1に記載の研磨液。
- 前記砥粒がセリウム系化合物を含む、請求項3に記載の研磨液。
- (A)ポリグリセリンを含有する、請求項1に記載の研磨液。
- 前記(A)成分の含有量が0.001~10質量%である、請求項5に記載の研磨液。
- (B)ヒドロキシアルキル基が結合した2以上の窒素原子を有する化合物を含有する、請求項1に記載の研磨液。
- 前記(B)成分がエチレンジニトリロテトラプロパノールを含む、請求項7に記載の研磨液。
- 前記(B)成分の含有量が0.001~5質量%である、請求項7に記載の研磨液。
- 下記一般式(1)で表される4-ピロン系化合物を含有する、請求項1に記載の研磨液。
[式中、X11、X12及びX13は、それぞれ独立に、水素原子又は1価の置換基である。] - 前記4-ピロン系化合物が、3-ヒドロキシ-2-メチル-4-ピロン、5-ヒドロキシ-2-(ヒドロキシメチル)-4-ピロン、及び、2-エチル-3-ヒドロキシ-4-ピロンからなる群より選ばれる少なくとも一種を含む、請求項10に記載の研磨液。
- 前記4-ピロン系化合物の含有量が0.001~5質量%である、請求項10に記載の研磨液。
- 飽和モノカルボン酸を含有する、請求項1に記載の研磨液。
- 請求項1~13のいずれか一項に記載の研磨液を用いて、Undoped Silicate Glassを含有する被研磨部材の被研磨面を研磨する工程を備える、研磨方法。
- 請求項14に記載の研磨方法により研磨された被研磨部材を用いて部品を得る、部品の製造方法。
- 請求項14に記載の研磨方法により研磨された被研磨部材を用いて半導体部品を得る、半導体部品の製造方法。
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| PCT/JP2023/003470 WO2024161614A1 (ja) | 2023-02-02 | 2023-02-02 | 研磨液、研磨方法、部品の製造方法、及び、半導体部品の製造方法 |
| CN202380036996.9A CN119096333A (zh) | 2023-02-02 | 2023-02-02 | 研磨液、研磨方法、零件的制造方法及半导体零件的制造方法 |
| EP23919751.0A EP4657505A1 (en) | 2023-02-02 | 2023-02-02 | Polishing liquid, polishing method, component production method, and semiconductor component production method |
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| TW202432748A (zh) | 2024-08-16 |
| KR20250139313A (ko) | 2025-09-23 |
| JPWO2024161614A1 (ja) | 2024-08-08 |
| EP4657505A1 (en) | 2025-12-03 |
| CN119096333A (zh) | 2024-12-06 |
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