WO2021144940A1 - 研磨剤、研磨剤用貯蔵液及び研磨方法 - Google Patents
研磨剤、研磨剤用貯蔵液及び研磨方法 Download PDFInfo
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- WO2021144940A1 WO2021144940A1 PCT/JP2020/001384 JP2020001384W WO2021144940A1 WO 2021144940 A1 WO2021144940 A1 WO 2021144940A1 JP 2020001384 W JP2020001384 W JP 2020001384W WO 2021144940 A1 WO2021144940 A1 WO 2021144940A1
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- Prior art keywords
- abrasive
- polishing
- allylamine
- insulating material
- group
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 219
- 238000000034 method Methods 0.000 title claims description 51
- 239000011550 stock solution Substances 0.000 title 1
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims abstract description 179
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- 239000006061 abrasive grain Substances 0.000 claims abstract description 58
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
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- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000000733 zeta-potential measurement Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Definitions
- the present invention relates to an abrasive, a storage solution for an abrasive, and a polishing method.
- CMP Chemical mechanical polishing
- Patent Document 1 semiconductor integrated circuits using a plurality of insulating materials have been proposed (for example, Patent Document 1 below).
- an insulating material having a low specific dielectric constant such as an organosilicon oxide (silicon oxide containing carbon; also referred to as “SiOC”) is used in the wiring process and does not contain carbon atoms.
- SiOC organosilicon oxide
- the excess portion of the organosilicon oxide is removed by CMP, and the underlying insulating material containing silicon (excluding the organosilicon oxide, for example, the silicon oxide containing no carbon atom, and the silicon oxide containing no carbon atom).
- a step of stopping polishing with a silicon nitride (which is generally used as a stopper material for CMP) is also conceivable.
- organic silicon oxide and silicon oxide that does not contain carbon atoms have very similar chemical compositions, so by utilizing an abrasive that can polish both materials and the hydrophobicity of carbon, silicon oxide can be obtained.
- Patent Documents 2 to 4 above Although there are abrasives that suppress the polishing of organic silicon oxide while polishing (for example, Patent Documents 2 to 4 above), they suppress the polishing of carbon atom-free silicon oxide while polishing the organic silicon oxide. It was difficult to develop an abrasive to be used.
- the present inventors have an effect of suppressing polishing on other insulating materials containing silicon, particularly silicon dioxide which is a silicon oxide containing no carbon atom (polishing).
- silicon dioxide which is a silicon oxide containing no carbon atom
- An object of the present invention is to solve the above problems, and an object of the present invention is to provide an abrasive, a storage solution for an abrasive, and a polishing method capable of selectively removing an organosilicon oxide with respect to silicon dioxide. ..
- abrasive grains containing silica and having a positive charge in an abrasive, and tertiary and / or quaternary allylamine-based polymers have a pH of 2.
- organic silicon oxide can be removed at a good polishing rate, and other insulating materials containing silicon (silicon oxide containing no carbon atom (silicon dioxide, etc.); We have found a composition that stops the polishing of silicon nitride, etc.).
- the abrasive according to the present invention polishes a substrate having an organic silicon oxide and an insulating material containing silicon (excluding organic silicon oxide) to remove at least a part of the organic silicon oxide.
- the abrasive contains abrasive grains containing silica and an allylamine-based polymer, the abrasive grains have a positive charge in the abrasive, and the allylamine-based polymer is 3. It is at least one selected from the group consisting of a secondary allylamine-based polymer and a quaternary allylamine-based polymer, and the pH of the abrasive is 2.8 to 5.0.
- the abrasive storage solution according to the present invention is an abrasive storage solution for obtaining the above-mentioned abrasive, and the abrasive can be obtained by diluting with water. In this case, the cost, space, and the like required for transporting and storing the abrasive can be reduced.
- the first embodiment of the polishing method according to the present invention is a step of preparing a substrate having an organosilicon oxide and an insulating material containing silicon (excluding an organosilicon oxide), and using the above-mentioned polishing agent. It comprises a polishing step of polishing the substrate to remove at least a part of the organosilicon oxide.
- a second embodiment of the polishing method according to the present invention includes a step of preparing a substrate having an organic silicon oxide and an insulating material containing silicon (excluding the organic silicon oxide), and the above-mentioned storage solution for an abrasive.
- the organosilicon oxide can be removed at a good polishing rate, and the organosilicon oxide can be selectively removed with respect to the insulating material other than the organosilicon oxide.
- an abrasive, a storage solution for an abrasive, and a polishing method capable of selectively removing an organosilicon oxide with respect to silicon dioxide.
- the organic silicon oxide is also applied to an insulating material containing silicon (silicon oxide containing no carbon atom, silicon nitride, etc., excluding organic silicon oxide) other than silicon dioxide. It is possible to provide a polishing agent, a storage solution for a polishing agent, and a polishing method that can be selectively removed. Further, according to the polishing agent, the storage solution for polishing agent and the polishing method of the present invention, the organosilicon oxide can be polished at a good polishing rate.
- the substrate having the organic silicon oxide and the insulating material containing silicon (excluding the organic silicon oxide) is polished to remove at least a part of the organic silicon oxide.
- abrasives or abrasive storage solutions can be provided. According to the present invention, it is possible to provide the use of an abrasive or an abrasive storage solution for double patterning.
- process includes not only an independent process but also a process in which the intended action of the process is achieved although it is not clearly distinguishable from other processes.
- the content of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. means.
- the "removal rate” means the rate at which the material to be polished is removed per unit time.
- selectively removing the material A with respect to the material B means that the material A is preferentially removed over the material B. More specifically, it means that the material A is preferentially removed over the material B in the substrate in which the material A and the material B are mixed.
- the mass of the abrasive is the amount of the storage solution for abrasives when the abrasive is obtained by adding water or the like to the storage solution for abrasives. It means a dilution such that it is X times the mass. For example, adding the same mass of water to the mass of the abrasive storage solution to obtain an abrasive is defined as diluting the abrasive storage solution by a factor of two.
- the abrasive according to the present embodiment is a composition that comes into contact with the surface to be polished during polishing, and is, for example, a polishing agent for chemical mechanical polishing (CMP).
- CMP chemical mechanical polishing
- the abrasive according to the present embodiment removes at least a part of the organosilicon oxide by chemically mechanically polishing a substrate having an organosilicon oxide and an insulating material containing silicon (excluding the organosilicon oxide). It is an abrasive for
- the abrasive according to the present embodiment contains at least silica-containing abrasive grains and an allylamine-based polymer.
- the abrasive grains have a positive charge with the abrasive, and the allylamine-based polymer is at least one selected from the group consisting of the tertiary allylamine-based polymer and the quaternary allylamine-based polymer, and the pH of the abrasive. Is 2.8 to 5.0.
- the organosilicon oxide is a carbon-containing silicon oxide, and is sometimes called "organic silicon oxide” or "carbon-containing silicon".
- the organosilicon oxide in the present specification has a carbon content of preferably 10 to 95 atm% as measured by the X-ray photoelectron spectroscopy (XPS) method.
- the carbon content of the organosilicon oxide is preferably 10 atm% or more, more preferably 15 atm% or more, still more preferably 20 atm% or more, from the viewpoint of effectively obtaining the effect of removing the organosilicon oxide at a high polishing rate. ..
- the carbon content of the organosilicon oxide is preferably 95 atm% or less, more preferably 93 atm% or less, still more preferably 91 atm% or less, from the viewpoint of effectively obtaining the effect of removing the organosilicon oxide at a high polishing rate. ..
- the carbon content of organosilicon oxide is measured by X-ray photoelectron spectroscopy.
- the analysis by X-ray photoelectron spectroscopy can be performed using, for example, "PHI-5000-VersaProbe II" manufactured by ULVAC PFI Co., Ltd.
- a monochromatic Al-K ⁇ ray (1486.6 eV) can be used as the X-ray source.
- the detection angle is 45 degrees
- the analysis area is 200 ⁇ m ⁇
- the voltage is 15 kV
- the output is 50 W.
- the carbon content is obtained by measuring the spectrum of C1s (280 to 300 eV), charging-correcting the obtained peak top of C1s as 284.3 eV, and obtaining the peak area of C1s.
- the organosilicon oxide is not particularly limited as long as it has at least a silicon atom, a carbon atom and an oxygen atom.
- the organosilicon oxide include low-k materials such as Black diamond series (manufactured by Applied Materials), Aurora, Coral, and organosilicate glasses, and Tamila Low-k materials.
- the method for forming the organosilicon oxide is not particularly limited, and examples thereof include a vapor deposition method and a spin coating method.
- the shape of the organosilicon oxide is not particularly limited, but is, for example, a film.
- the organosilicon oxide may be doped with an element such as phosphorus or boron.
- the insulating material containing silicon (hereinafter, may be simply referred to as "insulating material") other than the organosilicon oxide, and known materials can be widely used.
- the insulating material can also be said to be a silicon-based insulating material. More specifically, the insulating material includes silicon oxides such as silicon monoxide and silicon dioxide; silica-based materials such as fluorosilicate glass, silicon oxynitride (SiON), and silsesquioxane hydride; silicon carbide; Examples thereof include silicon nitrides such as silicon nitride.
- the insulating material may be doped with an element such as phosphorus or boron.
- the polishing rate of the organosilicon oxide tends to increase by using abrasive grains having a positive charge in the polishing agent.
- the abrasive grains containing silica have a higher affinity with the organosilicon oxide than other types of abrasive grains, and it is considered that the contact frequency with the organosilicon oxide increases. Therefore, it is considered that the polishing rate of the organosilicon oxide is increased by using the abrasive grains containing silica and having a positive charge in the abrasive.
- abrasive grains containing silica have a high affinity for insulating materials. Further, since the surface of the insulating material has a negative charge in a wide pH range, the abrasive grains having a positive charge in the abrasive are electrostatically adsorbed on the insulating material. Therefore, when abrasive grains containing silica and having a positive charge in the abrasive are used, not only the organosilicon oxide but also the polishing rate of the insulating material tends to increase.
- the polishing agent contains a predetermined allylamine-based polymer
- the present inventors can significantly reduce the polishing rate of the insulating material containing silicon (excluding organosilicon oxide), and the organosilicon oxide can be significantly reduced. It was found that the polishing rate of silicon was slightly reduced or hardly changed.
- the allylamine-based polymer is preferentially adsorbed on the surface of the insulating material containing silicon (excluding the organosilicon oxide) over the organosilicon oxide. Therefore, the protective film formed by the allylamine-based polymer is preferentially formed on the surface of the insulating material over the organosilicon oxide. As a result, the frequency of contact between the abrasive grains and the insulating material is reduced, and it is considered that the polishing rate of the insulating material is reduced.
- the organosilicon oxide can be removed at a good polishing rate, and the organosilicon oxide can be added to the insulating material containing silicon (excluding the organosilicon oxide). Can be selectively removed.
- a high polishing rate of the organosilicon oxide can be obtained, and a high polishing selectivity of the organosilicon oxide with respect to the insulating material containing silicon (excluding the organosilicon oxide) can be obtained.
- Abrasive rate of organosilicon oxide / Abrasive rate of insulating material containing silicon (excluding organosilicon oxide) can be obtained.
- the abrasive according to this embodiment contains abrasive grains containing silica.
- Abrasives have a positive charge in the abrasive. Since silica has a higher affinity for organosilicon oxide than other types of abrasive grains, it is considered that the frequency of contact between the abrasive grains and the organosilicon oxide increases when silica is used as the abrasive grains. ..
- Whether or not the abrasive grains have a positive charge in the abrasive can be determined by measuring the zeta potential of the abrasive grains in the abrasive. The zeta potential of the abrasive grains in the abrasive is measured, and if the value exceeds 0 mV, it can be determined that the abrasive grains have a positive charge.
- the zeta potential can be measured by, for example, the trade name: DELSA NANO C manufactured by Beckman Coulter.
- the zeta potential ( ⁇ [mV]) can be measured by the following procedure. First, in the zeta potential measuring device, the scattering intensity of the measurement sample is 1.0 ⁇ 10 4 to 5.0 ⁇ 10 4 cps (here, “cps” means counts per second, that is, count per second, and counts the particles. A sample is obtained by diluting the polishing agent with pure water so that the unit becomes). Then, the sample is placed in the zeta potential measurement cell and the zeta potential is measured. In order to adjust the scattering intensity to the above range, for example, the abrasive is diluted so that the abrasive grains are 1.7 to 1.8% by mass.
- Examples of the method for adjusting the abrasive grains so that they have a positive charge in the abrasive include a method for controlling the method for producing the abrasive grains, a method for adjusting the pH of the abrasive, and a method for surface-treating the abrasive grains. Be done.
- a case where silica is used as the abrasive grains will be described as an example.
- General silica has a negative charge in the liquid, but tends to have a positive charge by lowering the pH.
- silica can be surface-treated with a coupling agent having a cationic group.
- the zeta potential is preferably 10 mV or more, more preferably 15 mV or more, still more preferably 18 mV or more, from the viewpoint of obtaining a better polishing rate and storage stability.
- the upper limit of the zeta potential is not particularly limited, but is, for example, 100 mV.
- silica examples include colloidal silica and fumed silica. Among them, silica is used from the viewpoint that the polishing rate of the organosilicon oxide is further increased, the number of polishing scratches (referring to the scratches appearing on the surface to be polished after polishing) is small, and the particle size can be easily selected. Colloidal silica is preferred.
- Abrasive particles can contain particles other than silica.
- the abrasive grains may contain particles such as alumina, ceria, zirconia, hydroxide of cerium, and resin.
- the abrasive grains can be used individually by one type or in combination of two or more types.
- the silica content is preferably more than 50% by mass, more preferably 60% by mass or more, further preferably 70% by mass or more, based on the total mass of the abrasive grains, from the viewpoint of further increasing the polishing rate of the organosilicon oxide.
- 80% by mass or more is particularly preferable, 90% by mass or more is extremely preferable, and 95% by mass or more is very preferable.
- the content of silica is preferably 0.005 part by mass or more with respect to 100 parts by mass of the abrasive, from the viewpoint that sufficient mechanical polishing power can be easily obtained and the polishing rate of the organic silicon oxide is further increased.
- 05 parts by mass or more is more preferable, 0.10 parts by mass or more is further preferable, and 0.15 parts by mass or more is particularly preferable.
- the content of silica is 100 parts by mass of the abrasive from the viewpoint of easily avoiding an increase in the viscosity of the abrasive, easily avoiding agglomeration of abrasive grains, easily reducing polishing scratches, and easily handling the abrasive.
- 15 parts by mass or less is preferable, 10 parts by mass or less is more preferable, 5 parts by mass or less is further preferable, and 3 parts by mass or less is particularly preferable.
- the content of the abrasive grains is based on 100 parts by mass of the abrasive from the viewpoint that a sufficiently significant polishing rate of the organic silicon oxide can be easily obtained as compared with the polishing rate of the organic silicon oxide when the abrasive grains are not contained. , 0.01 part by mass or more, more preferably 0.05 part by mass or more, further preferably 0.1 part by mass or more, particularly preferably 0.5 part by mass or more, and extremely preferably 1 part by mass or more.
- the content of the abrasive grains is preferably 10 parts by mass or less, preferably 6 parts by mass or less, based on 100 parts by mass of the abrasive, from the viewpoint of improving the polishing rate of the organosilicon oxide and improving the dispersion stability of the abrasive grains.
- the following is more preferable, 4 parts by mass or less is further preferable, and 3 parts by mass or less is particularly preferable.
- the average particle size of the abrasive grains is preferably 10 nm or more, more preferably 30 nm or more, still more preferably 40 nm or more, from the viewpoint that sufficient mechanical polishing power can be easily obtained and the polishing rate of the organosilicon oxide is further increased.
- the average particle size of the abrasive grains is preferably 200 nm or less, more preferably 120 nm or less, still more preferably 90 nm or less, from the viewpoint of good dispersion stability of the abrasive grains.
- the average particle size of the abrasive grains can be measured by the photon correlation method. More specifically, for example, the average particle size can be measured with a device name manufactured by Malvern Instruments Co., Ltd .: Zetasizer 3000HS, a device name manufactured by Beckman Coulter Co., Ltd .: Delsa MAX Pro, or the like.
- the measurement method using Delsa MAX Pro is as follows. For example, an aqueous dispersion having an abrasive grain content adjusted to 0.2% by mass is prepared, and about 4 mL of this aqueous dispersion is placed in a 1 cm square cell (L indicates "liter"; the same applies hereinafter). , Install the cell in the device.
- the value obtained by setting the refractive index of the dispersion medium to 1.33, the viscosity to 0.887 mPa ⁇ s, and measuring at 25 ° C. can be adopted as the average particle size of the abrasive grains.
- the abrasive according to this embodiment contains an allylamine-based polymer.
- allylamine-based polymer is defined as a polymer having a structural unit obtained by polymerizing a monomer containing an allylamine-based compound.
- allylamine-based compound is defined as a compound having an allyl group and an amino group.
- the allylamine-based polymer may have a structural unit obtained by polymerizing only an allylamine-based compound, and has a structural unit obtained by copolymerizing an allylamine-based compound and a compound other than the allylamine-based compound. May be.
- the allylamine-based compound may be used alone or in combination of two or more.
- the allylamine-based polymer is selected from the tertiary allylamine-based polymer and the quaternary allylamine-based polymer from the viewpoint of facilitating the selective removal of organosilicon oxide from the insulating material.
- At least one selected from the group of The tertiary allylamine-based polymer or the quaternary allylamine-based polymer is a structural unit obtained by polymerizing a monomer containing an allyl group and a tertiary amino group, or an allylamine compound having an allyl group and a quaternary amino group. It is a polymer having.
- the weight average molecular weight of the allylamine-based polymer is preferably 500 or more, more preferably 800 or more, still more preferably 1000 or more, from the viewpoint of easily suppressing the polishing rate of the insulating material.
- the weight average molecular weight of the allylamine-based polymer is preferably 300,000 or less, more preferably 200,000 or less, still more preferably 150,000 or less, from the viewpoint of suppressing excessively high viscosity and obtaining good storage stability.
- the weight average molecular weight (Mw) of the allylamine-based polymer can be measured by, for example, gel permeation chromatography (GPC: Gel Permeation Chromatography) under the following conditions.
- the content of the allylamine-based polymer is preferably 0.001 part by mass or more, more preferably 0.003 part by mass or more, and 0. It is more preferably 004 parts by mass or more, and particularly preferably 0.005 parts by mass or more.
- the content of the allylamine-based polymer suppresses a decrease in the polishing rate of the organic silicon oxide, and from the viewpoint of easily maintaining a high polishing rate ratio of the organic silicon oxide to the insulating material with respect to 100 parts by mass of the polishing agent. , 0.4 parts by mass or less, more preferably 0.3 parts by mass or less, further preferably 0.2 parts by mass or less, particularly preferably 0.1 parts by mass or less, and extremely preferably 0.05 parts by mass or less.
- the mass ratio of the content of the allylamine-based polymer to the content of the abrasive grains is from the viewpoint of selectively removing the organic silicon oxide with respect to the insulating material. , Preferably 0.002 or more.
- the mass ratio is more preferably 0.003 or more, still more preferably 0.005 or more, from the viewpoint of easily removing the organosilicon oxide with respect to the insulating material.
- the mass ratio of the content of the allylamine-based polymer to the content of the abrasive grains is preferably 0.4 or less from the viewpoint of removing the organosilicon oxide at a good polishing rate.
- the mass ratio is more preferably 0.3 or less, and further preferably 0.2 or less, from the viewpoint that the organosilicon oxide can be easily removed at a good polishing rate.
- the allylamine-based polymer has a structural unit represented by the following formula (I) in the molecule of the polymer, the following formula (II). It is selected from the group consisting of the structural unit represented by the following formula (III), the structural unit represented by the following formula (IV), and the structural unit represented by the following formula (V). It is preferable to have at least one kind. In this case, since the allylamine-based polymer reduces the contact frequency between the insulating material and the abrasive grains, the polishing rate of the insulating material is further suppressed, so that the organosilicon oxide can be more selectively removed from the insulating material. ..
- R 11 and R 12 each independently represent an alkyl group or an aralkyl group, and the amino group may form an acid addition salt.
- R 2 represents an alkyl group or an aralkyl group, and the nitrogen-containing ring may form an acid addition salt.
- R 3 represents an alkyl group or an aralkyl group, and the nitrogen-containing ring may form an acid addition salt.
- R 41 and R 42 each independently represent an alkyl group or an aralkyl group, and D ⁇ represents a monovalent anion.
- R 51 and R 52 each independently represent an alkyl group or an aralkyl group, and D ⁇ represents a monovalent anion.
- the allylamine-based polymer may have one type alone or two or more types as the structural units (I) to (V).
- the total number of structural units (I) to (V) in the molecule is preferably 5 or more, more preferably 7 or more, still more preferably 10 or more, from the viewpoint of easily suppressing the polishing rate of the insulating material.
- the total number of structural units (I) to (V) in the molecule is an average value of allylamine-based polymers contained in the abrasive.
- the alkyl groups of R 11 , R 12 , R 2 and R 3 in formulas (I), (II) and (III) may be linear, branched or cyclic.
- the number of carbon atoms of the alkyl group is preferably 1 or more from the viewpoint of easily suppressing the polishing rate of the insulating material.
- the number of carbon atoms of the alkyl group is preferably 10 or less, more preferably 7 or less, further preferably 5 or less, and particularly preferably 4 or less, from the viewpoint of easily suppressing the polishing rate of the insulating material.
- the alkyl groups of R 11 , R 12 , R 2 and R 3 may have a hydroxyl group.
- Alkyl groups of R 11 , R 12 , R 2 and R 3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, tert-butyl group and cyclohexyl group. Examples thereof include hydroxyl group additions (3-hydroxypropyl group, etc.).
- An aralkyl group is a group in which one of the hydrogen atoms of an alkyl group is substituted with an aryl group.
- the alkyl group constituting the aralkyl group of R 11 , R 12 , R 2 and R 3 is any of linear, branched and cyclic. You may.
- the carbon number of the aralkyl group is preferably 7 to 10 from the viewpoint of easily suppressing the polishing rate of the insulating material.
- the aralkyl groups of R 11 , R 12 , R 2 and R 3 may have a hydroxyl group.
- Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylhexyl group, and hydroxyl group adducts thereof.
- the amino group in the formula (I) and the nitrogen-containing ring in the formulas (II) and (III) may form an acid addition salt.
- the acid addition salt include hydrochloride, hydrobromide, acetate, sulfate, nitrate, sulfite, phosphate, amidosulfate, methanesulfonate and the like.
- hydrochlorides, acetates and amidosulfates are preferable from the viewpoint of obtaining a higher polishing rate ratio of the organosilicon oxide to the insulating material.
- R 11 , R 12 , R 2 and R 3 are preferably methyl groups and ethyl groups from the viewpoint of good wettability with an insulating material (for example, silicon oxide).
- allylamine-based polymers having a structural unit represented by the formula (I), (II) or (III), the allylamine polymer and the allylamine polymer from the viewpoint of obtaining a higher polishing selectivity of the organosilicon oxide with respect to the insulating material.
- Dialylamine polymers are preferred.
- the structural unit containing the acid addition salt diallylamine hydrochloride, methyldiallylamine hydrochloride, ethyldiallylamine hydrochloride, methyldiallylamine acetate and methyldiallylamineamide sulfate are preferable.
- the alkyl groups of R 41 , R 42 , R 51 and R 52 in formulas (IV) and (V) may be linear, branched or cyclic.
- the number of carbon atoms of the alkyl groups of R 41 and R 42 is preferably 1 or more from the viewpoint of easily suppressing the polishing rate of the insulating material.
- the number of carbon atoms of the alkyl groups of R 41 and R 42 is preferably 10 or less, more preferably 7 or less, still more preferably 4 or less, from the viewpoint of easily suppressing the polishing rate of the insulating material.
- the number of carbon atoms of the alkyl groups of R 51 and R 52 is preferably 1 or more from the viewpoint of easily suppressing the polishing rate of the insulating material.
- the number of carbon atoms of the alkyl groups of R 51 and R 52 is preferably 10 or less, more preferably 7 or less, still more preferably 4 or less, from the viewpoint of easily suppressing the polishing rate of the insulating material.
- the alkyl groups of R 41 and R 42 may have a hydroxyl group.
- Alkyl groups of R 41 and R 42 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, tert-butyl group, cyclohexyl group, and hydroxyl group additions thereof (3). -Hydroxypropyl group, etc.) and the like.
- Examples of the alkyl group of R 51 and R 52 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a tert-butyl group and a cyclohexyl group.
- the alkyl group constituting the aralkyl group of R 41 , R 42 , R 51 and R 52 in the formulas (IV) and (V) may be linear, branched or cyclic.
- the carbon number of the aralkyl group is preferably 7 to 10 from the viewpoint of easily suppressing the polishing rate of the insulating material.
- the aralkyl groups of R 41 and R 42 may have a hydroxyl group.
- Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, and hydroxyl group adducts thereof.
- Examples of the aralkyl group of R 51 and R 52 include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group and the like.
- R 41 , R 42 , R 51 and R 52 are preferably a methyl group, a benzyl group and a phenethyl group from the viewpoint of good wettability with an insulating material (for example, silicon oxide).
- the partial structure represented by the following formula (IVa) in the formula (IV) and the partial structure represented by the following formula (Va) in the formula (V) include N, N-dialkylammonium salt and N-alkyl-. Examples include N-benzylammonium salt and the like. Examples of the N, N-dialkylammonium salt include N, N-dialkylammonium such as N, N-dimethylammonium halide, N, N-diethylammonium halide, N, N-dipropylammonium halide, and N, N-dibutylammonium halide.
- N N-dialkylammoniumalkylsulfate such as N, N-dimethylammoniummethylsulfate, N, N-methylethylammoniumethylsulfate and the like can be mentioned.
- N-alkyl-N-benzylammonium salt examples include N-alkyl-N-benzylammonium halides such as N-methyl-N-benzylammonium halide and N-ethyl-N-benzylammonium halide.
- the partial structural halide include chloride, bromide, and iodide.
- N, N-dimethylammonium chloride and N, N-methylethylammonium ethyl sulfate are preferable from the viewpoint of obtaining a higher polishing rate ratio of the organosilicon oxide to the insulating material.
- the allylamine-based polymer may have a structure obtained by copolymerizing an allylamine-based compound with a compound other than the allylamine-based compound.
- the allylamine-based polymer is, for example, a structural unit represented by the formula (I), a structural unit represented by the formula (II), a structural unit represented by the formula (III), and a structure represented by the formula (IV).
- the allylamine-based polymer has a structural unit represented by the following formula (VI), a structural unit represented by the following formula (VII), a structural unit represented by the following formula (VIII), and a following formula (IX). It may further have at least one selected from the group consisting of the represented structural units.
- an allylamine-based polymer has a structural unit represented by the formula (I), a structural unit represented by the formula (II), a structural unit represented by the formula (III), and a structure represented by the formula (IV).
- Q represents an alkylene group
- R 6 represents a hydrogen atom or an alkyl group
- n represents an average number of added moles of 0 to 30.
- R 8 represents a hydrogen atom or an alkyl group
- Y + represents a cation.
- R 9 represents a hydrogen atom or an alkyl group.
- examples of the monomer giving the structural unit represented by the formula (VI) include allyl alcohol and the like.
- examples of the monomer giving the structural unit represented by the formula (VI) when n is 1 to 30 include (poly) oxyalkylene monoallyl ether, (poly) oxyalkylene monoallyl monomethyl ether and the like.
- the alkylene group represented by Q a linear or branched alkylene group having 2 to 3 carbon atoms is preferable from the viewpoint of easily suppressing the polishing rate of the insulating material, and an ethylene group, a trimethylene group and a propylene group are preferable. Is more preferable.
- the alkylene group may be introduced alone or in combination of two or more.
- the R 6, from easily viewpoint to suppress the polishing rate of the insulating material a hydrogen atom and methyl group are preferable.
- a methyldiallylamine hydrochloride allyl alcohol copolymer is preferable from the viewpoint of further increasing the polishing rate ratio of the organosilicon oxide to the insulating material.
- Examples of the monomer giving the structural unit represented by the formula (VII) include sulfur dioxide and the like.
- a diallylamine hydrochloride sulfur dioxide copolymer is preferable from the viewpoint of obtaining a higher polishing rate ratio of the organosilicon oxide to the insulating material.
- Y + include alkali metal ions such as sodium ion and potassium ion; hydrogen ion; and ammonium ion.
- Examples of the monomer giving the structural unit represented by the formula (VIII) include maleic acid, fumaric acid, citraconic acid, itaconic acid, mesaconic acid, 2-allylmalonic acid, and the like.
- Maleic acid is preferable from the viewpoint of easy reduction and good dispersibility of the allylamine-based polymer in the abrasive.
- the allylamine-based polymer having the structural unit represented by the formula (VIII) includes a diallylamine hydrochloride maleic acid copolymer and diallylamine from the viewpoint of obtaining a higher polishing rate ratio of the organic silicon oxide to the insulating material.
- Amidosulfate maleic acid copolymer is preferable.
- R 9 in the formula (IX) a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable, from the viewpoint of easily suppressing the polishing rate of the insulating material.
- the monomer giving the structural unit represented by the formula (IX) include acrylamide and the like.
- the allylamine-based polymer having the structural unit represented by the formula (IX) includes a diallylmethylammonium chloride / acrylamide copolymer and a diallylmethylammonium chloride / acrylamide copolymer from the viewpoint of obtaining a higher polishing rate ratio of the organosilicon oxide to the insulating material.
- a diallyldimethylammonium chloride / acrylamide copolymer is preferable.
- a methyldiallylamine hydrochloride polymer, a methyldiallylamineamide sulfate polymer, and a diallyldimethylammonium chloride / acrylamide copolymer can be obtained from the viewpoint of obtaining a higher polishing rate ratio of the organic silicon oxide to the insulating material.
- Dialyldimethylammonium chloride polymer, and diallylamine hydrochloride sulfur dioxide copolymer are preferable.
- the abrasive according to this embodiment preferably contains water.
- Water is used as a dispersion medium or solvent for other components.
- the water preferably contains as little impurities as possible in order to suppress the inhibition of the action of other components.
- pure water and ultrapure water from which impurity ions have been removed with an ion exchange resin and then foreign substances have been removed through a filter, and distilled water are preferable.
- the abrasive according to the present embodiment is other than the abrasive grains and the above-mentioned allylamine-based polymer for the purpose of improving the dispersibility of the abrasive grains in the abrasive, improving the chemical stability of the abrasive, improving the polishing speed, and the like.
- Ingredients may be further contained.
- a component include additives such as an organic solvent, an acid component, a metal corrosion inhibitor (corrosion inhibitor), and an antifoaming agent.
- the content of the additive in the abrasive can be arbitrarily determined as long as the characteristics of the abrasive are not impaired.
- the abrasive according to this embodiment preferably further contains an acid component. Since the abrasive contains an acid component, the pH of the abrasive can be adjusted to a predetermined value. Since the polishing agent according to the present embodiment contains an acid component and the pH is controlled, the liquid stability of the polishing agent can be improved and the surface to be polished can be further flattened.
- the acid component is preferably at least one selected from the group consisting of organic acids and inorganic acids from the viewpoint of further improving the dispersibility, stability and polishing rate of the aqueous dispersion.
- the acid component may be an acid having no aromatic ring.
- Organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-Methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, glyco-licic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, maleic acid, malic acid, tartrate acid. , Citric acid and the like.
- the inorganic acid is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, and chromic acid.
- an organic acid is preferable from the viewpoint of suppressing corrosion of the metal wiring.
- the abrasive according to this embodiment may contain an organic solvent.
- the abrasive contains an organic solvent, the polishing rate ratio can be adjusted and the wettability of the abrasive can be improved. Further, when the polishing agent contains an organic solvent, the repulsion of the polishing particles is promoted, so that the aggregation of the polishing particles can be suppressed.
- the organic solvent is not particularly limited, but a solvent that is liquid at 20 ° C. is preferable.
- the solubility of the organic solvent in 100 g of water (20 ° C.) is preferably 30 g or more, more preferably 50 g or more, still more preferably 100 g or more, from the viewpoint of highly concentrating the abrasive.
- the organic solvent may be used alone or in combination of two or more.
- organic solvent examples include carbonate esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate; lactones such as butyrolactone and propyl lactone; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and triethylene glycol.
- Tripropylene glycol methanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, butanetriol, pentantriol, hexanetriol, heptanetriol, octanetriol, nonantriol, Glycols such as decantriol and erythritol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol mono Ethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol
- Glycol monoethers ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, dietile Glycol diethyl ether, dipropylene glycol diethyl ether, triethylene glycol diethyl ether, tripropylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, diethylene glycol dipropyl ether, dipropylene glycol dipropyl ether, triethylene glycol Dipropyl ether, tripropylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether
- glycols and derivatives of glycols are preferable from the viewpoint of low surface tension, and glycol monoethers are more preferable from the viewpoint of further lower surface tension.
- the content of the organic solvent is set to 100 parts by mass of the allylamine-based polymer from the viewpoint of suppressing the decrease in wettability of the abrasive with respect to the organosilicon oxide.
- 0.1 part by mass or more is preferable, 0.5 part by mass or more is more preferable, and 1 part by mass or more is further preferable.
- the content of the organic solvent is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less, based on 100 parts by mass of the allylamine-based polymer.
- the abrasive according to this embodiment may contain a metal anticorrosive agent. Since the abrasive contains a metal anticorrosive agent, when the substrate has metal wiring such as Co and Cu, vias, plugs, metal gates, etc., it suppresses metal corrosion when the metal wiring is exposed on the surface to be polished. Can be made to.
- the metal anticorrosive agent contained in the abrasive of the present embodiment is not particularly limited, and any conventionally known compound having an anticorrosive effect on metals can be used. Specifically, at least one selected from the group consisting of a triazole compound, a pyridine compound, a pyrazole compound, a pyrimidine compound, an imidazole compound, a guanidine compound, a thiazole compound, a tetrazole compound, a triazole compound and a hexamethylenetetramine can be used.
- compound is a general term for compounds having a skeleton thereof, and for example, a triazole compound means a compound having a triazole skeleton.
- the metal anticorrosive agent can be used alone or in combination of two or more.
- the content of the metal anticorrosive agent is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, from the viewpoint of suppressing metal corrosion. Further, from the viewpoint of suppressing a decrease in the polishing rate of the film to be polished, the content of the metal anticorrosive agent is preferably 5.0% by mass or less, and more preferably 0.5% by mass or less.
- the metal corrosion inhibitor makes it possible to suppress the etching rate of copper or cobalt-based metals even under severe temperature conditions (for example, 60 ° C.). It is considered that this is because it exerts a function as an excellent complex forming agent and a film protective agent.
- the metal anticorrosive agent at least one selected from the group consisting of triazole compounds, pyridine compounds, imidazole compounds, tetrazole compounds, triazine compounds and hexamethylenetetramine is preferable, and 3H-1,2,3- Triazolo [4,5-b] pyridine-3-ol, 1-hydroxybenzotriazole, 1H-1,2,3-triazolo [4,5-b] pyridine, benzotriazole, 5-methyl-1H-benzotriazole, etc.
- the pH of the abrasive according to the present embodiment is 2.8 to 5.0 from the viewpoint of facilitating the selective removal of the organosilicon oxide with respect to the insulating material.
- the pH of the abrasive is adjusted from the viewpoint of making it easier to selectively remove the organosilicon oxide from the insulating material, and from the viewpoint of easily obtaining sufficient mechanical polishing power and further improving the polishing rate of the organosilicon oxide. 2.9 or more is preferable, 3.0 or more is more preferable, and 3.1 or more is further preferable.
- the pH of the abrasive is preferably 4.8 or less, more preferably 4.5 or less, still more preferably 4.2 or less, from the viewpoint of suppressing aggregation of abrasive grains and obtaining good dispersion stability of abrasive grains. 4.0 or less is particularly preferable. From the above viewpoint, the pH of the abrasive is 2.8 to 4.8, 2.8 to 4.5, 2.8 to 4.2, 2.8 to 4.0, 3.0 to 4.8. , 3.0-4.5, 3.0-4.2, 3.0-4.0, 3.1-4.8, 3.1-4.5, 3.1-4.2, or It is preferably 3.1 to 4.0.
- the pH of the abrasive may be adjusted by, for example, the acid component; a base component such as ammonia, sodium hydroxide, potassium hydroxide, TMAH (tetramethylammonium hydroxide) or the like. pH is defined as pH at a liquid temperature of 25 ° C.
- the pH of the abrasive can be measured with a pH meter using a general glass electrode.
- a pH meter using a general glass electrode.
- the product name: Model (F-51) of HORIBA, Ltd. can be used.
- a phthalate pH standard solution (4.01), a neutral phosphate pH standard solution (pH 6.86), and a borate pH standard solution (pH 9.18) as pH standard solutions use a pH meter. It is obtained by calibrating at three points, putting the electrode of the pH meter in a polishing agent, and measuring the value after it has stabilized after 2 minutes or more.
- the liquid temperature of the standard buffer solution and the abrasive is, for example, 25 ° C.
- the method of blending and diluting the abrasive is not particularly limited, and each component can be dispersed or dissolved by, for example, stirring with a blade type stirrer, ultrasonic dispersion, or the like.
- the mixing order of each component with respect to water is not limited.
- the abrasive according to the present embodiment may be stored as a one-component abrasive containing at least the above-mentioned abrasive grains and the above-mentioned allylamine-based polymer, and may be stored as a slurry (first liquid) and an additive liquid (first liquid). It may be stored as a multi-component abrasive having (two liquids). In this case, the liquid stability of the abrasive can be improved.
- the constituent components of the polishing agent are divided into the slurry and the additive liquid so as to mix the slurry and the additive liquid to obtain the polishing agent.
- the slurry contains, for example, at least abrasive grains.
- the slurry may contain abrasive grains and water.
- the additive liquid contains, for example, at least an allylamine-based polymer.
- the additive liquid may contain an allylamine-based polymer and water.
- Additives such as an organic solvent, an acid component, a metal anticorrosive agent, and an antifoaming agent are preferably contained in the additive liquid among the slurry and the additive liquid.
- the constituent components of the abrasive may be stored in three or more liquids.
- the abrasive may be prepared by mixing the slurry and the additive liquid immediately before or during polishing.
- the slurry and the additive liquid in the multi-component polishing agent may be supplied onto the polishing surface plate, respectively, and the surface to be polished may be polished using the polishing agent obtained by mixing the slurry and the additive liquid on the polishing surface plate. ..
- the abrasive storage solution according to the present embodiment is a storage solution for obtaining the abrasive, and the abrasive can be obtained by diluting the abrasive storage solution with water.
- the storage liquid for an abrasive is stored with the amount of water reduced from that at the time of use, and is diluted with water before or during use to be used as the abrasive.
- the abrasive storage solution differs from the abrasive in that it contains less water than the abrasive.
- the dilution ratio is, for example, 1.5 times or more.
- the substrate having the organosilicon oxide and the insulating material containing silicon is polished, and the organosilicon oxide is selectively polished with respect to the insulating material.
- the substrate is, for example, an insulating material having recesses and protrusions on the surface (for example, an insulating material film) and an organosilicon oxide formed on the insulating material along the shape of the insulating material (for example, a film of an organosilicon oxide).
- the polishing may be chemical mechanical polishing (CMP).
- the polishing method according to the present embodiment may include, for example, as a polishing step, a polishing step of polishing the substrate with a one-component polishing agent to remove at least a part of the organic silicon oxide.
- a polishing step of polishing a substrate with a polishing agent obtained by mixing a slurry and an additive solution in a liquid polishing agent to remove at least a part of an organic silicon oxide may be provided, and storage for a polishing agent may be provided.
- a polishing step may be provided in which the substrate is polished with a polishing agent obtained by diluting the liquid with water to remove at least a part of the organic silicon oxide.
- the polishing may be chemical mechanical polishing (CMP).
- CMP chemical mechanical polishing
- the polishing method according to the present embodiment may include a step of preparing a substrate having an organosilicon oxide and an insulating material containing silicon (excluding the organosilicon oxide) before the polishing step.
- the polishing method according to the present embodiment includes an abrasive preparation step of mixing the slurry and the additive liquid in the multi-component abrasive to obtain the abrasive before the polishing step. You may.
- the polishing method according to the present embodiment may include an abrasive preparation step of diluting the abrasive storage liquid with water to obtain an abrasive before the polishing step.
- the surface to be polished of the substrate is pressed against the polishing cloth (polishing pad) of the polishing platen, and the polishing agent is supplied between the surface to be polished and the polishing cloth to supply the polishing agent to the back surface of the substrate (surface to be polished).
- the surface to be polished is polished by moving the substrate relative to the polishing platen while applying a predetermined pressure to the surface opposite to the polishing platen.
- the polishing apparatus for example, a general polishing apparatus having a surface plate to which a motor or the like capable of changing the rotation speed and a polishing pad can be attached and a holder for holding the substrate can be used.
- the polishing pad is not particularly limited, but a general non-woven fabric, polyurethane foam, porous fluororesin, or the like can be used.
- an abrasive is continuously supplied to the polishing cloth by a pump or the like.
- the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with the abrasive and the products produced by the progress of polishing are continuously discharged.
- the polishing method according to the present embodiment includes a polishing pad conditioning step before the polishing step.
- a dresser with diamond particles is used to condition the polishing pad with a liquid containing at least water.
- the polishing method according to the present embodiment preferably includes a substrate cleaning step after the polishing step. It is preferable that the substrate after polishing is thoroughly washed in running water, and then dried after removing water droplets adhering to the substrate by using spin dry or the like. Further, while flowing a commercially available cleaning solution on the surface of the substrate, the brush made of polyurethane is rotated and pressed against the substrate at a constant pressure to remove deposits on the substrate. The brush is cleaned by a known cleaning method and then dried. It is more preferable to let it.
- the substrate having the organosilicon oxide and the insulating material containing silicon (excluding the organosilicon oxide) is polished to remove at least a part of the organosilicon oxide.
- the polishing agent according to the present embodiment the polishing rate of the insulating material can be sufficiently reduced. Therefore, the substrate having the organosilicon oxide and the above-mentioned insulating material is polished to remove at least a part of the organosilicon oxide, and after a part of the insulating material is exposed, polishing hardly progresses. Can be done.
- Such an abrasive is a term that can be understood by those skilled in the art as "an abrasive that can remove an organosilicon oxide and stop polishing when an insulating material containing silicon (excluding an organosilicon oxide) is exposed". In other words.
- the polishing agent according to the present embodiment is used in a polishing method that requires a high polishing rate ratio of an organosilicon oxide to an insulating material containing silicon (excluding an organosilicon oxide) by utilizing the above-mentioned features. be able to. Specifically, the polishing method according to the present embodiment will be described with reference to FIG.
- a substrate having a substrate 11 and a silicon oxide 12 and a silicon nitride 13 having a predetermined pattern and formed on the substrate 11 is prepared (FIG. 1 (a)).
- the silicon oxide 12 and the silicon nitride 13 correspond to an insulating material containing silicon (excluding an organosilicon oxide).
- the organosilicon oxide 14 is coated or vapor-deposited on the substrate 11, the silicon oxide 12, and the silicon nitride 13, and further cured to form (FIG. 1 (b)).
- a pattern similar to the pattern of the silicon oxide 12 and the silicon nitride 13 is formed on the surface of the organosilicon oxide 14, a pattern similar to the pattern of the silicon oxide 12 and the silicon nitride 13 is formed.
- the pattern may be formed using only silicon oxide 12 or silicon nitride 13, or the pattern may be formed by other insulating materials.
- the surface layer portion of the organosilicon oxide 14 is polished (for example, CMP) until the silicon oxide 12 and the silicon nitride 13 are exposed, and the surface of the silicon oxide 12, the silicon nitride 13 and the organosilicon oxide are polished.
- a surface composed of 14 surfaces is flattened (FIG. 1 (c)).
- the polishing speed of the organosilicon oxide and the insulating material is preferably as follows from the viewpoint of being suitable for double patterning applications.
- the polishing rate of the organosilicon oxide is preferably 20 nm / min or more, more preferably 30 nm / min or more, from the viewpoint of shortening the polishing time.
- the polishing rate of the organosilicon oxide is 300 nm from the viewpoint that excessive polishing of the concave portions of the organosilicon oxide is suppressed to further improve the flatness and the polishing time can be easily adjusted. It is preferably less than / min, more preferably 200 nm / min or less, and even more preferably 100 nm / min or less.
- the polishing rate of the insulating material is preferably 10 nm / min or less, more preferably 5 nm / min or less, from the viewpoint that the polishing time can be easily adjusted.
- Double patterning is a patterning process in which the first pattern is formed by the first exposure and development, and then the second pattern is formed by the second exposure and development on the space portion of the first pattern. be.
- the polishing rate ratio of the organosilicon oxide to the insulating material is preferably 5 or more, more preferably 10 or more, from the viewpoint that polishing of the insulating material is suppressed and the surface of the substrate can be easily finished uniformly. 30 or more is more preferable.
- the polishing rate ratio is, for example, a polishing rate ratio when a blanket wafer having an organosilicon oxide formed on a substrate and a blanket wafer having an insulating material formed on the substrate are polished.
- the polishing speed ratio is, for example, the same polishing pad for each of the blanket wafer having the organosilicon oxide formed flat on the substrate and the blanket wafer having the insulating material formed flat on the substrate. , Can be evaluated by polishing at the same rotation speed and the same load.
- ⁇ Preparation of abrasive> (Example 1) Methyldiallylamine hydrochloride polymer (manufactured by Nittobo Medical Co., Ltd., PAS-M-1, weight average molecular weight: 20000. A tertiary allylamine-based polymer having a structural unit of formula (II). Hereinafter, "allylamine-based polymer 1". 0.01 part by weight and 0.6 part by weight of adipic acid (acid component) were placed in a container. Further, X parts by mass of ultrapure water was poured and then stirred to dissolve each component.
- Example 2 As the allylamine-based polymer, instead of the allylamine-based polymer 1, a diallyldimethylammonium chloride / acrylamide copolymer (manufactured by Nittobo Medical Co., Ltd., PAS-J-41, weight average molecular weight: 10000. Structural unit of formula (IV)) A quaternary allylamine-based polymer having the above (hereinafter referred to as “allylamine-based polymer 2”) was obtained in the same manner as in Example 1 except that 0.01 part by weight was used.
- allylamine-based polymer 2 A quaternary allylamine-based polymer having the above (hereinafter referred to as “allylamine-based polymer 2”) was obtained in the same manner as in Example 1 except that 0.01 part by weight was used.
- Example 3 As the allylamine-based polymer, instead of the allylamine-based polymer 1, it has a methyldiallylamine amide sulfate polymer (manufactured by Nittobo Medical Co., Ltd., PAS-22SA-40, weight average molecular weight: 15,000, structural unit of formula (II)). A polishing agent was obtained in the same manner as in Example 1 except that 0.01 part by weight of a tertiary allylamine-based copolymer (hereinafter referred to as “allylamine-based polymer 3”) was used.
- allylamine-based polymer 3 tertiary allylamine-based copolymer
- Example 4 As the allylamine-based polymer, instead of the allylamine-based polymer 1, a diallyldimethylammonium chloride polymer (manufactured by Nittobo Medical Co., Ltd., PAS-H-5L, weight average molecular weight: 30,000. A polishing agent was obtained in the same manner as in Example 1 except that 0.01 part by weight of a secondary allylamine-based copolymer (hereinafter referred to as “allylamine-based polymer 4”) was used.
- allylamine-based polymer 4 a secondary allylamine-based copolymer
- Example 5 An abrasive was obtained in the same manner as in Example 1 except that 0.02 parts by mass of the allylamine-based polymer 1 was used.
- Example 6 An abrasive was obtained in the same manner as in Example 1 except that 0.1 part by mass of acetic acid was used instead of adipic acid as the acid component.
- Example 7 An abrasive was obtained in the same manner as in Example 1 except that 0.1 part by mass of malic acid was used instead of adipic acid as the acid component.
- Example 8 An abrasive was obtained in the same manner as in Example 1 except that 0.1 part by mass of 5-methyl-1H-benzotriazole was used as the metal corrosion inhibitor.
- Example 1 An abrasive was obtained in the same manner as in Example 1 except that an allylamine-based polymer was not used.
- Example 2 An abrasive was obtained in the same manner as in Example 1 except that the pH of the abrasive was set to 7.8.
- Example 3 An abrasive was obtained in the same manner as in Example 1 except that 0.5 parts by mass of malic acid was used and the pH of the abrasive was 2.5.
- Example 4 The same as in Example 1 except that 0.01 parts by mass of a dimethylamine-ammonia-epichlorohydrin condensate (manufactured by Senka Co., Ltd., Unisense KHE100L), which is a primary allylamine-based polymer, was used instead of the allylamine-based polymer 1. Obtained an abrasive.
- a dimethylamine-ammonia-epichlorohydrin condensate manufactured by Senka Co., Ltd., Unisense KHE100L
- ⁇ Abrasive pH measurement> The pH of the abrasive was evaluated under the following conditions. The results are shown in Table 1. Measurement temperature: 25 ⁇ 5 ° C Measuring device: Product name of HORIBA, Ltd .: Model (F-51) Measuring method: A phthalate pH standard solution (4.01), a neutral phosphate pH standard solution (pH 6.86), and a borate pH standard solution (pH 9.18) were used as pH standard solutions. After calibrating the pH meter at three points, the electrode of the pH meter was put into a polishing agent, and the pH after lapsed for 2 minutes or more and stabilized was measured by the measuring device.
- a film (also referred to as a SiOC film) of an organic silicon oxide having a thickness of 100 nm and a carbon content of 89 atm% measured by an X-ray photoelectron spectroscopy (XPS) method is formed on a silicon substrate as a substrate to be polished.
- a substrate obtained by forming (referred to) on a silicon substrate by a CVD method was used.
- Each of the substrates cut into 2 cm squares was fixed to a holder to which a suction pad for attaching a substrate of a polishing device (Nanofactor Co., Ltd., FACT-200) was attached.
- the holder was placed on a surface plate on which a polyurethane foam polishing cloth was attached, with the material to be polished containing SiOC facing down.
- a weight was placed so that the processing load was 0.34 kgf / cm 2.
- the polishing rate was calculated from the film thickness difference obtained by measuring the film thickness before and after polishing.
- a film thickness measuring device F40 manufactured by Filmometrics Co., Ltd. was used for measuring the film thickness. Further, the polishing rate ratio was calculated by dividing the polishing rate of the SiOC film by the polishing rate of the insulating material film. The results are shown in Table 1.
- Corrosion evaluation of the Co film was performed on the assumption that the substrate has Co metal wiring.
- a blanket substrate (a) in which a cobalt layer having a thickness of 200 nm was formed by a PVD method on a 12-inch silicon substrate was prepared.
- the blanket substrate (a) was cut into a 20 mm square chip to prepare an evaluation chip (b).
- the evaluation chips (b) were placed in beakers containing 50 g of each of the abrasives, and immersed in a constant temperature bath at 60 ° C. for 1 minute.
- the evaluation chip (b) after immersion was taken out, thoroughly washed with pure water, and then blown with nitrogen gas to dry the water on the chip.
- the resistance of the evaluation chip (b) after drying was measured with a resistivity meter, and converted to the film thickness of the cobalt layer after immersion by the following formula (1).
- a calibration curve was obtained from the resistance value information corresponding to each film thickness of the blanket substrate (a), and the film thickness of the cobalt layer was obtained from the following formula (1).
- Film thickness of cobalt layer after immersion [nm] 1291.9 ⁇ (resistance value [m ⁇ ] of evaluation chip (b)) ⁇ (-0.8658) / 10 ...
- the etching rate of the cobalt layer was determined from the following formula (2) from the obtained film thickness of the cobalt layer after immersion and the thickness of the cobalt layer before immersion.
- Cobalt layer etching rate (Co-ER) [nm / min] (Cobalt layer film thickness before immersion [nm] -Cobalt layer film thickness after immersion [nm]) / 1 minute ...
- Substrate, 12 Silicon oxide, 13 . Silicon nitride, 14 . Organosilicon oxide.
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Abstract
Description
本明細書において「工程」との語には、独立した工程だけでなく、他の工程と明確に区別できないもののその工程の所期の作用が達成される工程が含まれる。
本実施形態に係る研磨剤は、研磨時に被研磨面に触れる組成物であり、例えば化学機械研磨(CMP)用研磨剤である。
本実施形態に係る研磨剤は、シリカを含む砥粒を含有する。砥粒は、研磨剤中で正の電荷を有している。他の種類の砥粒と比較してシリカの有機ケイ素酸化物への親和性が高いことから、砥粒としてシリカを用いた場合、砥粒と有機ケイ素酸化物との接触頻度が増加すると考えられる。
本実施形態に係る研磨剤は、アリルアミン系重合体を含有する。本明細書において「アリルアミン系重合体」とは、アリルアミン系化合物を含む単量体を重合して得られる構造単位を有する重合体として定義される。本明細書において「アリルアミン系化合物」とは、アリル基及びアミノ基を有する化合物として定義される。アリルアミン系重合体は、アリルアミン系化合物のみを重合して得られる構造単位を有していてもよく、アリルアミン系化合物と、アリルアミン系化合物以外の化合物とを共重合して得られる構造単位を有していてもよい。アリルアミン系化合物は、一種類を単独で、又は二種類以上を組み合わせて使用できる。
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、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、商品名「GS-220HQ」、「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/分
測定時間:45分
本実施形態に係る研磨剤は、好ましくは水を含有する。水は、他の成分の分散媒、又は、溶媒として用いられる。水としては、他の成分の作用を阻害することを抑制するために不純物を可能な限り含有しないものが好ましい。具体的には、水としては、イオン交換樹脂にて不純物イオンを除去した後にフィルタを通して異物を除去した純水及び超純水、並びに、蒸留水が好ましい。
本実施形態に係る研磨剤は、研磨剤中の砥粒の分散性の向上、研磨剤の化学的安定性の向上、研磨速度の向上等の目的で、砥粒及び上記のアリルアミン系重合体以外の成分を更に含有してもよい。このような成分としては、有機溶媒、酸成分、金属防食剤(腐食防止剤)、消泡剤等の添加剤が挙げられる。添加剤の研磨剤中の含有量は、研磨剤の特性を損なわない範囲で任意に決定できる。
本実施形態に係る研磨剤は、好ましくは酸成分を更に含有する。研磨剤が酸成分を含有することにより、研磨剤のpHを所定の値に調整できる。本実施形態に係る研磨剤が酸成分を含有してpHが制御されることにより、研磨剤の液状安定性を高めることができると共に被研磨面を更に良好に平坦化できる。酸成分は、水系分散体の分散性、安定性及び研磨速度を更に向上させることができる観点から、有機酸及び無機酸からなる群より選択される少なくとも一種が好ましい。酸成分は、芳香環を有しない酸であってもよい。有機酸としては、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、2-メチル酪酸、n-ヘキサン酸、3,3-ジメチル酪酸、2-エチル酪酸、4-メチルペンタン酸、n-ヘプタン酸、2-メチルヘキサン酸、n-オクタン酸、2-エチルヘキサン酸、グリコ-ル酸、グリセリン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、マレイン酸、リンゴ酸、酒石酸、クエン酸等が挙げられる。無機酸としては、特に制限はないが、塩酸、硫酸、硝酸、クロム酸等が挙げられる。被研磨表面にコバルトなどの金属配線が露出している場合、金属配線の腐食抑制の観点から、有機酸の方が好ましい。
本実施形態に係る研磨剤は、有機溶媒を含有してもよい。研磨剤が有機溶媒を含有することにより、研磨速度比を調整できると共に研磨剤の濡れ性を向上させることができる。また、研磨剤が有機溶媒を含有することにより、研磨粒子の反発を促進させることで、研磨粒子の凝集を抑制させることもできる。有機溶媒としては、特に制限はないが、20℃で液状の溶媒が好ましい。100gの水(20℃)に対する有機溶媒の溶解度は、研磨剤を高濃縮化する観点から、30g以上が好ましく、50g以上がより好ましく、100g以上が更に好ましい。有機溶媒は、一種類又は二種類以上を組み合わせて使用できる。
本実施形態に係る研磨剤は、金属防食剤を含有してもよい。研磨剤が金属防食剤を含有することにより、Co、Cu等の金属配線、ビア、プラグ、メタルゲートなどを基体が有する場合において、金属配線が被研磨面に露出した際の金属の腐食を抑制させることができる。
本実施形態に係る研磨剤のpHは、絶縁材料に対して有機ケイ素酸化物を選択的に除去し易くする観点から、2.8~5.0である。研磨剤のpHは、絶縁材料に対して有機ケイ素酸化物を更に選択的に除去し易くする観点、及び充分な機械的研磨力が得られ易く有機ケイ素酸化物の研磨速度が更に向上する観点から、2.9以上が好ましく、3.0以上がより好ましく、3.1以上が更に好ましい。研磨剤のpHは、砥粒の凝集を抑制して砥粒の良好な分散安定性が得られる観点から、4.8以下が好ましく、4.5以下がより好ましく、4.2以下が更に好ましく、4.0以下が特に好ましい。上記の観点から、研磨剤のpHは、2.8~4.8、2.8~4.5、2.8~4.2、2.8~4.0、3.0~4.8、3.0~4.5、3.0~4.2、3.0~4.0、3.1~4.8、3.1~4.5、3.1~4.2、又は3.1~4.0であることが好ましい。研磨剤のpHは、例えば、前記酸成分;アンモニア、水酸化ナトリウム、水酸化カリウム、TMAH(テトラメチルアンモニウムヒドロキシド)等の塩基成分などにより調整してもよい。pHは液温25℃におけるpHと定義する。
本実施形態に係る研磨剤用貯蔵液は、前記研磨剤を得るための貯蔵液であり、研磨剤用貯蔵液を水で希釈することにより前記研磨剤が得られる。研磨剤用貯蔵液は、水の量を使用時よりも減じて保管されており、使用前又は使用時に水で希釈されて前記研磨剤として用いられる。研磨剤用貯蔵液は、水の含有量が前記研磨剤よりも少ない点で前記研磨剤と異なっている。希釈倍率は、例えば1.5倍以上である。
次に、本実施形態に係る研磨方法について説明する。
(実施例1)
メチルジアリルアミン塩酸塩重合体(ニットーボーメディカル株式会社製、PAS-M-1、重量平均分子量:20000。式(II)の構造単位を有する3級アリルアミン系重合体。以下、「アリルアミン系重合体1」という)0.01質量部と、アジピン酸(酸成分)0.6質量部とを容器に入れた。さらに、超純水X質量部を注いだ後に撹拌して各成分を溶解させた。次に、平均粒子径が70nmであるコロイダルシリカを2.00質量部添加して研磨剤100質量部を得た。砥粒の表面は、研磨剤中において正に帯電していた。なお、超純水の配合量X質量部は、研磨剤が100質量部になるよう計算して調整した。
アリルアミン系重合体として、アリルアミン系重合体1に代えて、ジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体(ニットーボーメディカル株式会社製、PAS-J-41、重量平均分子量:10000。式(IV)の構造単位を有する4級アリルアミン系重合体。以下、「アリルアミン系重合体2」という)0.01質量部を用いたこと以外は実施例1と同様にして研磨剤を得た。
アリルアミン系重合体として、アリルアミン系重合体1に代えて、メチルジアリルアミンアミド硫酸塩重合体(ニットーボーメディカル株式会社製、PAS-22SA-40、重量平均分子量:15000。式(II)の構造単位を有する3級アリルアミン系共重合体。以下、「アリルアミン系重合体3」という)0.01質量部を用いたこと以外は実施例1と同様にして研磨剤を得た。
アリルアミン系重合体として、アリルアミン系重合体1に代えて、ジアリルジメチルアンモニウムクロリド重合体(ニットーボーメディカル株式会社製、PAS-H-5L、重量平均分子量:30000。式(IV)の構造単位を有する4級アリルアミン系共重合体。以下、「アリルアミン系重合体4」という)0.01質量部を用いたこと以外は実施例1と同様にして研磨剤を得た。
アリルアミン系重合体1を0.02質量部用いたこと以外は実施例1と同様にして研磨剤を得た。
酸成分としてアジピン酸の代わりに酢酸を0.1質量部用いたこと以外は実施例1と同様にして研磨剤を得た。
酸成分としてアジピン酸の代わりにリンゴ酸を0.1質量部用いたこと以外は実施例1と同様にして研磨剤を得た。
金属防食剤として5-メチル-1H-ベンゾトリアゾールを0.1質量部用いたこと以外は実施例1と同様にして研磨剤を得た。
アリルアミン系重合体を用いないこと以外は実施例1と同様にして研磨剤を得た。
研磨剤のpHを7.8としたこと以外は実施例1と同様にして研磨剤を得た。
リンゴ酸を0.5質量部用いて、研磨剤のpHを2.5とした以外は実施例1と同様にして研磨剤を得た。
アリルアミン系重合体1に代えて、1級アリルアミン系重合体であるジメチルアミン-アンモニア-エピクロルヒドリン縮合物(センカ株式会社製、ユニセンスKHE100L)を0.01質量部用いた以外は実施例1と同様にして研磨剤を得た。
研磨剤のpHを下記の条件で評価した。結果を表1に示す。
測定温度:25±5℃
測定装置:株式会社堀場製作所の商品名:Model(F-51)
測定方法:フタル酸塩pH標準液(4.01)と、中性リン酸塩pH標準液(pH6.86)と、ホウ酸塩pH標準液(pH9.18)とをpH標準液として用い、pHメータを3点校正した後、pHメータの電極を研磨剤に入れて、2分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。
被研磨対象の基体として、X線光電子分光(XPS)法により測定される炭素量が89atm%である厚み100nmの有機ケイ素酸化物の膜(SiOC膜ともいう)をシリコン基板上に形成して得られる基体と、厚み1000nmの二酸化ケイ素膜(絶縁材料膜)をシリコン基板上にCVD法で形成して得られる基体と、厚み200nmのケイ素窒化物の膜(絶縁材料膜。Si3N4膜ともいう)をシリコン基板上にCVD法で形成して得られる基体と、を用いた。研磨装置(株式会社ナノファクター製、FACT-200)の基体取り付け用吸着パッドを貼り付けたホルダーに、2cm角に切断した前記各基体を固定した。発泡ポリウレタンの研磨布を貼り付けた定盤上に、SiOCを含む被研磨材料面を下にしてホルダーを載せた。加工荷重が0.34kgf/cm2になるように重しを載せた。定盤上に研磨剤を15mL/分で滴下しながら、定盤回転数を90分-1に設定し、SiOC膜、二酸化ケイ素膜、Si3N4膜を60秒間研磨した。
基体がCoの金属配線を有する場合を想定して、Co膜に対する腐食評価を実施した。12インチのシリコン基板上に、PVD法で厚み200nmのコバルト層を形成したブランケット基板(a)を用意した。上記ブランケット基板(a)を、20mm角のチップに切り出して評価用チップ(b)を用意した。
浸漬後のコバルト層の膜厚[nm]=1291.9×(評価用チップ(b)の抵抗値[mΩ])^(-0.8658)/10・・・(1)
そして、得られた浸漬後のコバルト層の膜厚と浸漬前のコバルト層の厚みから、下記式(2)より、コバルト層のエッチング速度を求めた。
コバルト層のエッチング速度(Co-ER)[nm/分]=(浸漬前のコバルト層の膜厚[nm]-浸漬後のコバルト層の膜厚[nm])/1分・・・(2)
Claims (13)
- 有機ケイ素酸化物と、ケイ素を含む絶縁材料(前記有機ケイ素酸化物を除く)と、を有する基体を研磨して、前記有機ケイ素酸化物の少なくとも一部を除去するための研磨剤であって、
シリカを含む砥粒と、アリルアミン系重合体と、を含有し、
前記砥粒が前記研磨剤中で正の電荷を有し、
前記アリルアミン系重合体が、3級アリルアミン系重合体、及び4級アリルアミン系重合体からなる群より選択される少なくとも一種であり、
前記研磨剤のpHが2.8~5.0である、研磨剤。 - 前記アリルアミン系重合体が、下記式(I)で表される構造単位、下記式(II)で表される構造単位、下記式(III)で表される構造単位、下記式(IV)で表される構造単位、及び下記式(V)で表される構造単位からなる群より選択される少なくとも一種を有する、請求項1に記載の研磨剤。
- 前記シリカがコロイダルシリカである、請求項1又は2に記載の研磨剤。
- 酸成分を更に含有する、請求項1~3のいずれか一項に記載の研磨剤。
- 有機溶媒を更に含有する、請求項1~4のいずれか一項に記載の研磨剤。
- 金属防食剤を更に含有する、請求項1~5のいずれか一項に記載の研磨剤。
- 前記研磨剤のpHが3.0~4.0である、請求項1~6のいずれか一項に記載の研磨剤。
- 前記絶縁材料に対する前記有機ケイ素酸化物の研磨速度比が5以上である、請求項1~7のいずれか一項に記載の研磨剤。
- 前記砥粒を含む第一の液と、
前記アリルアミン系重合体を含む第二の液と、を有する複数液式研磨剤として保存される、請求項1~8のいずれか一項に記載の研磨剤。 - 請求項1~9のいずれか一項に記載の研磨剤を得るための研磨剤用貯蔵液であって、
水で希釈することにより前記研磨剤が得られる、研磨剤用貯蔵液。 - 有機ケイ素酸化物と、ケイ素を含む絶縁材料(前記有機ケイ素酸化物を除く)と、を有する基体を用意する工程と、
請求項1~9のいずれか一項に記載の研磨剤を用いて前記基体を研磨して、前記有機ケイ素酸化物の少なくとも一部を除去する研磨工程と、を備える、研磨方法。 - 有機ケイ素酸化物と、ケイ素を含む絶縁材料(前記有機ケイ素酸化物を除く)と、を有する基体を用意する工程と、
請求項10に記載の研磨剤用貯蔵液を水で希釈して前記研磨剤を得る工程と、
前記研磨剤を用いて前記基体を研磨して、前記有機ケイ素酸化物の少なくとも一部を除去する研磨工程と、を備える、研磨方法。 - 前記研磨工程において前記絶縁材料が露出したときに研磨を停止する、請求項11又は12に記載の研磨方法。
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JP5493526B2 (ja) | 2009-07-14 | 2014-05-14 | 日立化成株式会社 | Cmp用研磨液及び研磨方法 |
-
2020
- 2020-01-16 US US17/792,227 patent/US20230094224A1/en active Pending
- 2020-01-16 KR KR1020227025240A patent/KR20220117323A/ko unknown
- 2020-01-16 JP JP2021570585A patent/JP7327518B2/ja active Active
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JP2009206316A (ja) * | 2008-02-28 | 2009-09-10 | Fujifilm Corp | 研磨液 |
JP2017110219A (ja) * | 2015-12-14 | 2017-06-22 | 日立化成株式会社 | 研磨液、研磨液セット及び基体の研磨方法 |
JP2017139350A (ja) * | 2016-02-04 | 2017-08-10 | 日立化成株式会社 | 研磨液、研磨液セット、及び、基体の研磨方法 |
JP2019059921A (ja) * | 2017-09-26 | 2019-04-18 | 株式会社フジミインコーポレーテッド | 研磨用組成物、研磨用組成物の製造方法、研磨方法および半導体基板の製造方法 |
JP2019163420A (ja) * | 2018-03-20 | 2019-09-26 | 株式会社フジミインコーポレーテッド | 研磨用組成物およびそれを用いた研磨方法 |
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JPWO2021144940A1 (ja) | 2021-07-22 |
KR20220117323A (ko) | 2022-08-23 |
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