WO2018055985A1 - 研磨用組成物、ならびにこれを用いた研磨方法および半導体基板の製造方法 - Google Patents
研磨用組成物、ならびにこれを用いた研磨方法および半導体基板の製造方法 Download PDFInfo
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- WO2018055985A1 WO2018055985A1 PCT/JP2017/030786 JP2017030786W WO2018055985A1 WO 2018055985 A1 WO2018055985 A1 WO 2018055985A1 JP 2017030786 W JP2017030786 W JP 2017030786W WO 2018055985 A1 WO2018055985 A1 WO 2018055985A1
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- Prior art keywords
- polishing
- polishing composition
- acid
- accelerator
- abrasive grains
- Prior art date
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
-
- 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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Definitions
- the present invention relates to a polishing composition, a polishing method using the same, and a method for manufacturing a semiconductor substrate.
- the present invention mainly relates to a polishing composition preferably used for polishing a semiconductor substrate such as a silicon wafer, a polishing method using the same, and a method for manufacturing a semiconductor substrate.
- CMP chemical mechanical polishing
- Precise polishing using a polishing liquid is performed on the surface of materials such as metal, metalloid, nonmetal, and oxides thereof.
- the surface of a silicon wafer used as a component of a semiconductor product is generally finished to a high-quality mirror surface through a lapping process (rough polishing process) and a polishing process (precision polishing process).
- the polishing process typically includes a preliminary polishing process (preliminary polishing process) and a final polishing process (final polishing process).
- a polishing composition used in polishing a silicon wafer generally contains abrasive grains and a polishing accelerator such as an alkali compound.
- a polishing composition used for polishing a silicon wafer Patent Document 1 discloses a polishing composition for a silicon wafer containing water, silica particles, an alkali compound, a water-soluble polymer compound, and polyethylene glycol. ing.
- the present invention has been made in view of the above problems, and an object thereof is to provide a polishing composition that can effectively improve the polishing rate of an object to be polished.
- the present inventor has conducted intensive research to solve the above problems. As a result, it was found that the above problems can be solved by using a polishing composition containing abrasive grains, a polishing accelerator having a nucleophilic parameter of 14.5 to 30 and water, and completed the present invention. It was.
- the nucleophilic parameter is represented by the following formula (1).
- a polishing composition capable of effectively improving the polishing rate of an object to be polished.
- the polishing composition of the present invention contains abrasive grains, a polishing accelerator having a nucleophilic parameter represented by the following formula (1) of 14.5 to 30 and water.
- the polishing rate of an object to be polished can be effectively improved.
- the mechanism for obtaining such an effect is considered as follows. However, the following mechanism is just a guess, and the scope of the present invention is not limited thereby.
- the object to be polished is a silicon wafer
- Si (OH) x generated by nucleophilic reaction between silicon atoms and hydroxide ions (OH ⁇ ) and further hydrolysis by protons is generated. It is considered that the removal proceeds by scraping by mechanical action of abrasive grains or the like, or by dissolution by reaction with OH ⁇ . From this, it is considered that an important chemical reaction in polishing of an object to be polished is a nucleophilic reaction.
- the present inventor has found that a polishing composition containing a polishing accelerator having a nucleophilic parameter represented by the above (1) in a specific range is a polishing object.
- the present inventors have found that the polishing rate can be effectively improved.
- the polishing accelerator having a nucleophilic parameter represented by the above formula (1) of 14.5 or more and 30 or less is a compound exhibiting nucleophilicity, and the polishing accelerator interacts with the surface of the object to be polished. It is considered that the covalent bond distance between atoms on the surface of the polishing object can be extended and the covalent bond can be weakened. Accordingly, it is considered that the polishing of the object to be polished is facilitated by the scraping by the mechanical action of the abrasive grains and the removal by the dissolution, and the polishing rate is improved.
- the polishing composition of the present invention using a compound having a nucleophilic parameter in the range of 14.5 or more and 30 or less as a polishing accelerator can effectively improve the polishing rate of an object to be polished.
- the polishing composition of the present invention contains abrasive grains, a polishing accelerator having a nucleophilic parameter represented by the above formula (1) of 14.5 or more and 30 or less, and water.
- a polishing accelerator having a nucleophilic parameter represented by the above formula (1) of 14.5 or more and 30 or less and water.
- the polishing composition of the present invention essentially contains abrasive grains.
- the abrasive grains contained in the polishing composition have an action of mechanically polishing the object to be polished.
- the abrasive used may be any of inorganic particles, organic particles, and organic-inorganic composite particles.
- the inorganic particles include particles made of metal oxides such as silica, alumina, ceria, titania, silicon nitride particles, silicon carbide particles, and boron nitride particles.
- Specific examples of the organic particles include polymethyl methacrylate (PMMA) particles.
- PMMA polymethyl methacrylate
- silica is preferable, and colloidal silica is particularly preferable.
- Abrasive grains may be surface-modified. Since ordinary colloidal silica has a zeta potential value close to zero under acidic conditions, silica particles are not electrically repelled with each other under acidic conditions and are likely to agglomerate. In contrast, abrasive grains whose surfaces are modified so that the zeta potential has a relatively large negative value even under acidic conditions are strongly repelled from each other and dispersed well even under acidic conditions. As a result, the storage stability of the polishing composition can be improved.
- Such surface-modified abrasive grains can be obtained, for example, by mixing a metal such as aluminum, titanium or zirconium or an oxide thereof with the abrasive grains and doping the surface of the abrasive grains. Further, the surface-modified abrasive grains may be colloidal silica obtained by chemically bonding a functional group of an organic acid to the surface of the abrasive grains and fixing an organic acid.
- the lower limit of the average primary particle diameter of the abrasive grains is preferably 10 nm or more, more preferably 15 nm or more, and further preferably 20 nm or more.
- the upper limit of the average primary particle diameter of the abrasive grains is preferably 200 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less.
- the polishing rate of the object to be polished by the polishing composition is further improved, and the occurrence of defects on the surface of the object to be polished after polishing with the polishing composition is further suppressed. be able to.
- the average primary particle diameter of an abrasive grain is calculated based on the specific surface area of the abrasive grain measured by BET method, for example.
- the lower limit of the average secondary particle diameter of the abrasive grains is preferably 15 nm or more, more preferably 20 nm or more, and further preferably 30 nm or more.
- the upper limit of the average secondary particle diameter of the abrasive grains is preferably 300 nm or less, more preferably 260 nm or less, and further preferably 220 nm or less.
- the secondary particles referred to here are particles formed by association of abrasive grains in the polishing composition, and the average secondary particle diameter of the secondary particles is measured by, for example, a dynamic light scattering method. be able to.
- the lower limit of the content of the abrasive grains in the polishing composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 0.5% by mass or more. Further preferred. Further, the upper limit of the content of the abrasive grains in the polishing composition is preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 5% by mass or less. Within such a range, the polishing rate of the polishing object can be further improved, the cost of the polishing composition can be reduced, and the surface of the polishing object after polishing with the polishing composition can be reduced. It is possible to further suppress the occurrence of defects.
- the polishing composition according to one embodiment of the present invention essentially contains water as a dispersion medium (solvent) in order to disperse or dissolve each component.
- the dispersion medium may be a mixed solvent of water and an organic solvent for dispersing or dissolving each component.
- organic solvent examples include acetone, acetonitrile, ethanol, methanol, isopropanol, glycerin, ethylene glycol, propylene glycol and the like, which are organic solvents miscible with water.
- these organic solvents may be used without being mixed with water, and each component may be dispersed or dissolved and then mixed with water. These organic solvents can be used alone or in combination of two or more.
- water does not contain impurities as much as possible from the viewpoint of inhibiting the contamination of the object to be cleaned and the action of other components.
- water for example, water having a total content of transition metal ions of 100 ppb or less is preferable.
- the purity of water can be increased by operations such as removal of impurity ions using an ion exchange resin, removal of foreign matters by a filter, distillation, and the like.
- deionized water ion exchange water
- pure water ultrapure water, distilled water, or the like is preferably used as the water.
- the polishing composition of the present invention contains a polishing accelerator (hereinafter also simply referred to as a polishing accelerator) having a nucleophilic parameter represented by the following formula (1) of 14.5 or more and 30 or less.
- the nucleophilic parameter is a parameter used as an index indicating the strength of nucleophilicity of a compound. From the test of amine reactivity with several benzhydryl derivatives having known electrophilicity, Calculated by equation (1). Moreover, since the polishing composition of the present invention essentially contains water, the nucleophilic parameter in the present invention is a value in water. In the present specification, the value of the nucleophilic parameter is specifically described in the reactivity parameter database (Mayr's Database of Reactivity Parameters) of Dr. Herbert Mayr of Ludwig-Maximilians-Universitat Munchen. (URL: http://www.cup.lmu.de/oc/mayr/reactionsdatebank2/). The value of the nucleophilic slope parameter is also described in the database.
- the polishing accelerator used in the polishing composition of the present invention has a nucleophilic parameter of 14.5 or more and 30 or less.
- Such a polishing accelerator is thought to be capable of extending the covalent bond distance between atoms on the surface of the polishing object and weakening the covalent bond by interacting with the surface of the polishing object. Therefore, it is considered that the polishing of the object to be polished is facilitated by the scraping by the mechanical action of the abrasive grains and the removal by the above-described dissolution, and the polishing rate is improved.
- the nucleophilic parameter is preferably 16.5 or more, more preferably 17.0 or more, and even more preferably 17.5 or more, 18.2 The above is particularly preferable.
- the nucleophilic parameter is preferably 24.0 or less, and more preferably 23.0 or less.
- the nucleophilic parameter is preferably 14.5 or more and 24.0 or less, more preferably 14.5 or more and 23.0 or less, and 18.2 or more. More preferably, it is 23.0 or less.
- the type of the polishing accelerator used in the polishing composition of the present invention is not particularly limited as long as the nucleophilic parameter is 14.5 or more and 30 or less.
- it may be a compound such as an inorganic acid, an organic acid, an amine, or an amino acid, or a salt thereof.
- the inorganic acid or salt thereof having a nucleophilic parameter of 14.5 or more and 30 or less include sulfurous acid and sodium sulfite.
- Examples of the organic acid having a nucleophilic parameter of 14.5 or more and 30 or less include mercaptocarboxylic acid. Among mercaptocarboxylic acids, mercaptoacetic acid is preferable.
- Examples of the amine having a nucleophilic parameter of 14.5 or more and 30 or less include dimethylamine, monomethylhydrazine, or cyclic amines such as piperazine, piperidine, hexamethyleneimine, and the like.
- a cyclic amine having 7 to 10 ring members is preferable, and hexamethyleneimine is more preferable.
- amino acids having a nucleophilic parameter of 14.5 or more and 30 or less include cysteine, proline and the like.
- a polishing accelerator may be used independently and may use multiple types together.
- the polishing accelerator used in the polishing composition of the present invention is at least one selected from the group consisting of cyclic amines having 7 to 10 ring members and mercaptocarboxylic acid.
- the cyclic amine is hexamethyleneimine.
- Hexamethyleneimine exhibits high stability in neutral to alkaline environments, and since hexamethyleneimine is difficult to adsorb on abrasive grains, each component in the polishing composition containing hexamethyleneimine is further stabilized. Thus, the polishing rate can be kept constant at a high level.
- the mercaptocarboxylic acid is mercaptoacetic acid.
- mercaptoacetic acid exhibits high stability in a neutral to alkaline environment, and since mercaptoacetic acid is difficult to adsorb to abrasive grains, each component in the polishing composition containing mercaptoacetic acid Is more stabilized and the polishing rate can be kept constant at a high level.
- the content of the polishing accelerator contained in the polishing composition is not particularly limited, but is preferably 0.1% by mass or more with respect to the entire polishing composition. From the viewpoint of further effectively improving the polishing rate, the content of the polishing accelerator is more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more.
- the upper limit of the content of the polishing accelerator contained in the polishing composition is not particularly limited, but is preferably 5.0% by mass or less from the viewpoint of maintaining the surface quality of the object to be polished. The content is more preferably at most mass%, further preferably at most 1.0 mass%.
- the content of the polishing accelerator refers to the kind of content when a kind of polishing accelerator is used alone. When two or more kinds of polishing accelerators are used in combination, it means the total content of two or more kinds of polishing accelerators.
- the polishing composition of the present invention essentially contains abrasive grains, a polishing accelerator having a nucleophilic parameter represented by the above formula (1) of 14.5 to 30 and water, but in addition to the above components And may contain other additives. Here, it does not restrict
- the polishing composition of the present invention can further contain a pH adjuster.
- the pH can be adjusted by adding an appropriate amount of a pH adjusting agent.
- the pH adjuster used as necessary to adjust the pH of the polishing composition to a desired value may be either acid or alkali, and may be either an inorganic compound or an organic compound. Good.
- the acid include, for example, inorganic acids such as sulfuric acid, nitric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid and phosphoric acid; formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid , N-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycol Acids, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid and lactic acid and other carboxylic acids, and methanesulf
- alkali examples include alkali metal hydroxides or salts thereof such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, amines, quaternary ammonium salts and the like. These pH regulators can be used alone or in combination of two or more.
- the pH of the polishing composition according to one embodiment of the present invention is preferably 7.0 or more from the viewpoint of further improving the polishing rate of the object to be polished.
- the pH of the polishing composition according to the present invention is more preferably 9.0 or more, and further preferably 10.0 or more.
- the upper limit of the pH of the polishing composition of the present invention is not particularly limited, but is preferably 12.0 or less from the viewpoint of economy and handling safety of the polishing composition, and preferably 11.0 or less. More preferably.
- pH of polishing composition uses the pH meter (For example, Horiba, Ltd.
- LAQUA (trademark)
- standard buffer solution phthalate pH buffer solution [pH: 4.01 (25)] ° C)
- neutral phosphate pH buffer [pH: 6.86 (25 ° C)
- carbonate pH buffer [pH: 10.01 (25 ° C)]
- antiseptics and fungicides that may be included in the polishing composition if necessary include, for example, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazoline-3 -Isothiazoline preservatives such as ON, paraoxybenzoates, phenoxyethanol and the like. These antiseptics and fungicides may be used alone or in combination of two or more.
- the polishing composition of the present invention may be a one-component type or a multi-component type including a two-component type.
- the polishing composition of the present invention may be prepared by diluting the stock solution of the polishing composition, for example, 10 times or more using a diluent such as water.
- the polishing object to be polished using the polishing composition according to one embodiment of the present invention is not particularly limited, and examples include polishing objects having various materials and shapes.
- the material of the object to be polished is, for example, silicon material, aluminum, nickel, tungsten, steel, tantalum, titanium, stainless steel or other metal or semimetal, or alloys thereof; quartz glass, aluminosilicate glass, glassy carbon Glass materials such as; ceramic materials such as alumina, silica, sapphire, silicon nitride, tantalum nitride, titanium carbide; compound semiconductor substrate materials such as silicon carbide, gallium nitride, gallium arsenide; resin materials such as polyimide resin; Can be mentioned.
- polishing target object may be comprised with several material among the said materials.
- a polishing object containing a silicon material is preferable. That is, it is preferable that the polishing composition according to one embodiment of the present invention is used for polishing a polishing object including a silicon material.
- the silicon material preferably includes at least one material selected from the group consisting of silicon single crystal, amorphous silicon, and polysilicon.
- the silicon material is more preferably a silicon single crystal or polysilicon, and particularly preferably a silicon single crystal, from the viewpoint that the effects of the present invention can be obtained more remarkably. That is, in one embodiment of the present invention, the polishing object is preferably a polishing object including single crystal silicon, and more preferably a single crystal silicon substrate (silicon wafer).
- the shape of the object to be polished is not particularly limited.
- the polishing composition according to the present invention can be preferably applied to polishing a polishing object having a flat surface such as a plate shape or a polyhedron shape.
- the method for producing the polishing composition of the present invention is not particularly limited, and can be obtained, for example, by stirring and mixing abrasive grains, a polishing accelerator and, if necessary, other additives in water as a dispersion medium. it can. Moreover, when adding the pH adjuster containing a dispersion medium (water), an abrasive grain, a polishing accelerator, and other additives as needed are stirred and mixed in the pH adjuster containing a dispersion medium (water). A method may be adopted.
- the temperature at which the abrasive grains and each component are mixed is not particularly limited, but is preferably 10 to 40 ° C. and may be heated to increase the dissolution rate. Further, the mixing time is not particularly limited as long as uniform mixing can be performed.
- the polishing composition of the present invention is suitably used for polishing a polishing object containing single crystal silicon, particularly a single crystal silicon substrate (silicon wafer). That is, in one embodiment of the present invention, there is provided a polishing composition used for polishing a polishing object containing single crystal silicon. In another embodiment, a polishing composition used for polishing a single crystal silicon substrate (silicon wafer) is provided.
- the present invention also provides a polishing method for polishing an object to be polished containing single crystal silicon using the polishing composition of the present invention.
- a polishing method for polishing a single crystal silicon substrate using the polishing composition of the present invention is also provided.
- the present invention also provides a method for manufacturing a semiconductor substrate including a step of polishing an object to be polished containing single crystal silicon by the polishing method.
- a method of manufacturing a semiconductor substrate including a step of polishing a single crystal silicon substrate by the polishing method is also provided.
- the polishing step in the polishing method according to the present invention is not particularly limited as long as it is a step of polishing a single crystal silicon substrate, but is preferably a chemical mechanical polishing (CMP) step.
- the polishing step may be a polishing step consisting of a single step or a polishing step consisting of a plurality of steps.
- a polishing process consisting of a plurality of processes for example, a process of performing a final polishing process after a preliminary polishing process (rough polishing process), a secondary polishing process of one or more times after a primary polishing process, The process etc. which perform a final polishing process after that are mentioned.
- polishing apparatus used in the polishing method according to the present invention, a polishing surface plate on which a holder for holding a semiconductor substrate and the like, a motor capable of changing the number of rotations, and the like are attached and a polishing pad (polishing cloth) can be attached.
- a general polishing apparatus having the following can be used.
- the polishing apparatus any of a small table polishing machine, a single-side polishing apparatus, or a double-side polishing apparatus may be used.
- polishing pad a general nonwoven fabric, polyurethane, porous fluororesin, or the like can be used without particular limitation. It is preferable that the polishing pad is grooved so that the polishing liquid accumulates.
- the polishing conditions are not particularly limited.
- the rotational speed of the polishing platen (platen) is preferably 10 to 500 rpm.
- the rotational speed of the head (carrier) is preferably 10 to 500 rpm.
- the pressure applied to the substrate having the object to be polished is preferably 0.5 to 10 psi.
- the method of supplying the polishing composition to the polishing pad is not particularly limited, and for example, a method of continuously supplying with a pump or the like is employed. Although there is no restriction
- the polishing time is not particularly limited, it is preferably 5 seconds or more and 180 seconds or less for the step using the polishing composition.
- the substrate After completion of polishing, the substrate is washed in running water, and water droplets adhering to the substrate are removed by a spin dryer or the like, and dried to obtain a semiconductor substrate.
- the average secondary particle size of the abrasive grains was measured using a dynamic light scattering type particle size / particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., model number: UPA UT-151). First, abrasive grains were dispersed in pure water to prepare a dispersion having a loading index (laser scattering intensity) of 0.01. Next, using this dispersion, the value of the volume average particle diameter Mv (value of D50) in the UT mode was measured, and the obtained value was defined as the average secondary particle diameter.
- polishing composition [Example 1] (Preparation of polishing composition (A-1)) Colloidal silica (average primary particle size 35 nm, average secondary particle size 63 nm) 0.5% by mass in water, sodium sulfite 0.05 mol / L as polishing accelerator, potassium hydroxide as pH adjuster Were added in an amount of pH 10.5 and mixed to prepare a polishing composition (A-1).
- Example 2 to 6 and Comparative Examples 1 to 5 Preparation of polishing compositions (A-2) to (A-6) and (C-1) to (C-5)) Each polishing composition was prepared in the same manner as in Example 1 except that the type of polishing accelerator and the type of pH adjuster were changed as shown in Table 1 below (mixing temperature: about 25 ° C. , Mixing time: about 10 minutes).
- nucleophilic parameters of polishing accelerator The nucleophilic parameter of each polishing accelerator is expressed by the following formula (1).
- Polishing device small table polishing machine (Eng 380IN, manufactured by Nippon Engis Co., Ltd.) Polishing pad: Rigid polyurethane pad (Nitta Haas, IC1000) Platen rotation speed: 60 [rpm] Head (carrier) rotation speed: 60 [rpm] Polishing pressure: 3.0 [psi] Polishing composition (slurry) flow rate: 100 [ml / min] Polishing time: 1 [min] (3) Measurement of polishing rate The polishing rate was measured by the following procedure.
- the thickness change ⁇ d Si (m) of the object to be polished before and after polishing was divided by the polishing time t (min), and the unit was further converted to ( ⁇ / min). This value was defined as the polishing rate v Si ( ⁇ / min).
- Adsorption of polishing accelerator to silica (abrasive grains) was measured by the following method. Specifically, first, a polishing accelerator was added to a 1% by mass silica (abrasive) aqueous solution so as to be 0.05 mol / L. Thereafter, the adsorption reaction was promoted by storing at 80 ° C. in an air bath. One week later, after taking out and cooling, the solid-liquid was separated with a centrifuge (16,000 rpm for 1 hour), and only the supernatant was collected. The collected supernatant was measured for the residual amount of the polishing accelerator with a total carbon measuring device (TOC-5000A, manufactured by Shimadzu Corporation). The results are summarized in Table 1. Those with a residual amount of 80% or more are marked with ⁇ , and those with a residual amount of less than 80% are marked with ⁇ .
- TOC-5000A total carbon measuring device
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- Manufacturing & Machinery (AREA)
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- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
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Citations (10)
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JPS52112192A (en) * | 1976-03-16 | 1977-09-20 | Nakano Kiyoshi | Grinding agent for metals |
JPH09137155A (ja) * | 1995-11-16 | 1997-05-27 | Tokyo Ohka Kogyo Co Ltd | 研磨用組成物および研磨方法 |
JP2002030276A (ja) * | 2000-05-12 | 2002-01-31 | Kao Corp | 研磨液組成物 |
JP2003507895A (ja) * | 1999-08-13 | 2003-02-25 | キャボット マイクロエレクトロニクス コーポレイション | 停止化合物を伴う化学機械的研磨系及びその使用方法 |
JP2006156825A (ja) * | 2004-11-30 | 2006-06-15 | Kao Corp | 半導体基板用研磨液組成物 |
JP2008147651A (ja) * | 2006-12-05 | 2008-06-26 | Cheil Industries Inc | シリコンウエハの最終研磨用スラリー組成物、及びそれを用いたシリコンウエハの最終研磨方法 |
WO2009025383A1 (ja) * | 2007-08-23 | 2009-02-26 | Nitta Haas Incorporated | 研磨組成物 |
WO2009096495A1 (ja) * | 2008-02-01 | 2009-08-06 | Fujimi Incorporated | 研磨用組成物及びそれを用いた研磨方法 |
WO2012005289A1 (ja) * | 2010-07-08 | 2012-01-12 | 株式会社Sumco | シリコンウェーハの研磨方法およびその研磨液 |
WO2012141145A1 (ja) * | 2011-04-13 | 2012-10-18 | 株式会社 フジミインコーポレーテッド | 基板のエッジ研磨用組成物及びそれを用いた基板のエッジ研磨方法 |
-
2017
- 2017-08-28 WO PCT/JP2017/030786 patent/WO2018055985A1/ja active Application Filing
- 2017-08-28 JP JP2018540930A patent/JP6916192B2/ja active Active
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Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS52112192A (en) * | 1976-03-16 | 1977-09-20 | Nakano Kiyoshi | Grinding agent for metals |
JPH09137155A (ja) * | 1995-11-16 | 1997-05-27 | Tokyo Ohka Kogyo Co Ltd | 研磨用組成物および研磨方法 |
JP2003507895A (ja) * | 1999-08-13 | 2003-02-25 | キャボット マイクロエレクトロニクス コーポレイション | 停止化合物を伴う化学機械的研磨系及びその使用方法 |
JP2002030276A (ja) * | 2000-05-12 | 2002-01-31 | Kao Corp | 研磨液組成物 |
JP2006156825A (ja) * | 2004-11-30 | 2006-06-15 | Kao Corp | 半導体基板用研磨液組成物 |
JP2008147651A (ja) * | 2006-12-05 | 2008-06-26 | Cheil Industries Inc | シリコンウエハの最終研磨用スラリー組成物、及びそれを用いたシリコンウエハの最終研磨方法 |
WO2009025383A1 (ja) * | 2007-08-23 | 2009-02-26 | Nitta Haas Incorporated | 研磨組成物 |
WO2009096495A1 (ja) * | 2008-02-01 | 2009-08-06 | Fujimi Incorporated | 研磨用組成物及びそれを用いた研磨方法 |
WO2012005289A1 (ja) * | 2010-07-08 | 2012-01-12 | 株式会社Sumco | シリコンウェーハの研磨方法およびその研磨液 |
WO2012141145A1 (ja) * | 2011-04-13 | 2012-10-18 | 株式会社 フジミインコーポレーテッド | 基板のエッジ研磨用組成物及びそれを用いた基板のエッジ研磨方法 |
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