WO2011118505A1 - 研磨パッドおよびその製造方法、ならびに半導体デバイスの製造方法 - Google Patents
研磨パッドおよびその製造方法、ならびに半導体デバイスの製造方法 Download PDFInfo
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- WO2011118505A1 WO2011118505A1 PCT/JP2011/056455 JP2011056455W WO2011118505A1 WO 2011118505 A1 WO2011118505 A1 WO 2011118505A1 JP 2011056455 W JP2011056455 W JP 2011056455W WO 2011118505 A1 WO2011118505 A1 WO 2011118505A1
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- Prior art keywords
- polishing
- polishing pad
- compound
- polyurethane foam
- layer
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- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
- B24B37/11—Lapping tools
- B24B37/20—Lapping pads for working plane surfaces
- B24B37/24—Lapping pads for working plane surfaces characterised by the composition or properties of the pad materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
- C08G18/2835—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds having less than 5 ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
Definitions
- the present invention stabilizes flattening processing of optical materials such as lenses and reflection mirrors, silicon wafers, glass substrates for hard disks, aluminum substrates, and materials that require high surface flatness such as general metal polishing processing.
- the present invention also relates to a polishing pad that can be performed with high polishing efficiency, a method for manufacturing the same, and a method for manufacturing a semiconductor device.
- the polishing pad of the present invention is particularly useful for finish polishing of a silicon wafer or glass.
- mirror polishing of semiconductor wafers such as silicon wafers, lenses, and glass substrates mainly involves rough polishing mainly for adjusting the flatness and in-plane uniformity, and improving surface roughness and removing scratches. There is intended finish polishing.
- a suede-like artificial leather made of soft polyurethane foam is usually applied to a rotatable surface plate, and a wafer containing colloidal silica is supplied to an alkali-based aqueous solution. This is done by rubbing (Patent Document 1).
- Patent Document 2 describes a polishing cloth that is intended to reduce micro-waviness generated on the surface of an object to be polished, and has a polyurethane foam on the surface layer.
- a specific composition or composition of the polyurethane foam does not describe a specific composition or composition of the polyurethane foam, and there is room for further improvement in terms of the effect of reducing microwaviness.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a polishing pad capable of reducing microwaviness generated on the surface of an object to be polished, a method for manufacturing the same, and a method for manufacturing a semiconductor device. There is.
- the polishing pad according to the present invention is a polishing pad having a polishing layer made of a thermosetting polyurethane foam
- the thermosetting polyurethane foam contains an isocyanate component and an active hydrogen-containing compound as raw material components
- the active hydrogen-containing compound contains a polyol compound having 2 or more functional groups and a monool compound having 1 functional group.
- the polishing layer is composed of a thermosetting polyurethane foam, and contains a polyol compound having 2 or more functional groups as a raw material component and a monool compound having 1 functional group. To do.
- the polishing pad having such a configuration exhibits a durability due to the thermosetting polyurethane foam, and contains a monool compound having a functional group number of 1 so that micro waviness generated on the surface of the polishing object is generated. Can be reduced.
- the monool compound has the following general formula (1): R 1 — (OCH 2 CHR 2 ) n —OH (1) (Wherein R 1 is a methyl group or an ethyl group, R 2 is a hydrogen atom or a methyl group, and n is an integer of 1 to 5).
- R 1 is a methyl group or an ethyl group
- R 2 is a hydrogen atom or a methyl group
- n is an integer of 1 to 5
- the polishing pad preferably contains 1 to 20 parts by weight of the monool compound with respect to 100 parts by weight of the polyol compound.
- the polishing pad preferably contains 20 to 75 parts by weight of a polyol compound having 3 to 4 functional groups and a hydroxyl value of 100 to 1900 in 100 parts by weight of the polyol compound.
- a monool compound having a functional group number of 1 is used as a raw material for a thermosetting polyurethane foam, the polyurethane molecular weight is low, and the polishing layer is low in hardness so that polishing characteristics such as polishing speed can be obtained. There is a tendency to get worse.
- by adjusting the content of the polyol compound within such a range it is possible to reduce the microwaviness generated on the surface of the object to be polished while maintaining the hardness of the polishing layer.
- the isocyanate component is preferably aromatic isocyanate, more preferably carbodiimide-modified diphenylmethane diisocyanate.
- the active hydrogen-containing compound and the carbodiimide-modified MDI are used in combination, the adhesion between the polishing layer and the base material layer is remarkably improved when the base material layer is laminated on the polishing layer.
- the thermosetting polyurethane foam has substantially spherical cells having an average cell diameter of 20 to 300 ⁇ m.
- the durability of the polishing layer can be improved by forming the polishing layer with a thermosetting polyurethane foam having substantially spherical cells with an average cell diameter of 20 to 300 ⁇ m. Therefore, when the polishing pad of the present invention is used, the planarization characteristic can be kept high for a long time, and the stability of the polishing rate is also improved.
- the substantially spherical shape means a spherical shape and an elliptical shape.
- Oval and spherical bubbles are those having a major axis L to minor axis S ratio (L / S) of 5 or less, preferably 3 or less, more preferably 1.5 or less.
- the present invention also relates to a cell-dispersed urethane containing, as a raw material component, an active hydrogen-containing compound containing a polyol compound having 2 or more functional groups, a monool compound having 1 functional group, and an isocyanate component.
- a step of preparing the composition by a mechanical foaming method a step of applying the cell-dispersed urethane composition on a face material, and curing the cell-dispersed urethane composition, thereby forming substantially spherical cells having an average cell diameter of 20 to 300 ⁇ m.
- the present invention relates to a method for producing a polishing pad comprising a step of forming a polishing layer comprising a thermosetting polyurethane foam and a step of uniformly adjusting the thickness of the polishing layer. According to this manufacturing method, it is possible to manufacture a polishing pad that can reduce microwaviness generated on the surface of the object to be polished.
- the present invention relates to a method for manufacturing a semiconductor device including a step of polishing the surface of a semiconductor wafer using any of the polishing pads described above.
- the polishing pad of the present invention has a polishing layer made of a thermosetting polyurethane foam (hereinafter also referred to as “polyurethane foam”).
- Polyurethane resin is excellent in abrasion resistance, and it is possible to easily obtain polymers having desired physical properties by changing the raw material composition. Also, it is easy to form almost spherical fine bubbles by mechanical foaming (including mechanical flossing). Since it can be formed, it is a particularly preferable material as a constituent material of the polishing layer.
- the polyurethane resin is obtained using an isocyanate component and an active hydrogen-containing compound (such as a polyol compound having a functional group number of 2 or more, a monool compound having 1 functional group and a polyamine compound) as raw material components.
- an active hydrogen-containing compound such as a polyol compound having a functional group number of 2 or more, a monool compound having 1 functional group and a polyamine compound
- the isocyanate component a known compound in the field of polyurethane can be used without particular limitation.
- aromatic diisocyanates are preferably used, and carbodiimide-modified MDI is particularly preferably used.
- polyol compound having 2 or more functional groups examples include those usually used in the technical field of polyurethane.
- examples include polyether polyols typified by polytetramethylene ether glycol and polyethylene glycol, polyester polyols typified by polybutylene adipate, reaction products of polyester glycols such as polycaprolactone polyol and polycaprolactone and alkylene carbonate, etc.
- examples of the polyol compound having 2 or more functional groups include trimethylolpropane, glycerin, diglycerin, 1,2,6-hexanetriol, triethanolamine, pentaerythritol, tetramethylolcyclohexane, and methylglucoside.
- alkylene oxides ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4- Low butanediol, 2,3-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, etc.
- Molecular weight polyol, monoethanolamine, diethanolamine may contain an alcohol amine such as 2- (2-aminoethylamino) ethanol, and mono-propanolamine. These may be used alone or in combination of two or more.
- a chain extender may be contained as a polyol compound having 2 or more functional groups.
- the chain extender is an organic compound having at least two active hydrogen groups, and examples of the active hydrogen group include a hydroxyl group, a primary or secondary amino group, and a thiol group (SH).
- the total amount of the polyol compound when the total amount of the polyol compound is 100 parts by weight, it is preferable to contain 20 to 75 parts by weight of a polyol compound having a functional group number of 3 to 4 and a hydroxyl value of 100 to 1900.
- R 1 (OCH 2 CHR 2 ) n —OH (1)
- R 1 is a methyl group or an ethyl group
- R 2 is a hydrogen atom or a methyl group
- n is an integer of 1 to 5
- Micro waviness generated on the surface can be further reduced.
- Ether ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polyethylene glycol mono-p-isooctylphenyl ether; acetic acid, acrylic acid, methacrylic acid, etc.
- alkylene oxide adducts of carboxylic acids alkylene oxide adducts of carboxylic acids.
- a polyamine compound may be contained as the active hydrogen-containing compound.
- examples of polyamine compounds include ethylenediamine, tolylenediamine, diphenylmethanediamine, and alkylene oxide (EO, PO, etc.) adducts thereof. These may be used alone or in combination of two or more. It is particularly preferable to use an EO adduct of ethylenediamine.
- Polyurethane resin can be produced by either the prepolymer method or the one-shot method.
- a chain extender is used for curing the isocyanate-terminated prepolymer.
- the chain extender those described above can be used.
- the ratio of the isocyanate component and the active hydrogen-containing compound can be variously changed depending on the molecular weight of each and the desired physical properties of the polyurethane foam.
- the number of isocyanate groups (NCO INDEX) of the isocyanate component relative to the total number of active hydrogen groups (hydroxyl group + amino group) of the active hydrogen-containing compound is 0.80 to 1.20. It is preferably 0.90 to 1.15. When the number of isocyanate groups is outside this range, curing failure occurs and the required specific gravity, hardness, compression rate, etc. tend not to be obtained.
- the polyurethane resin can be produced by applying a known urethanization technique such as a melting method or a solution method, but is preferably produced by a melting method in consideration of cost, working environment, and the like.
- thermosetting polyurethane foam constituting the polishing layer can be preferably produced by a mechanical foaming method (including a mechanical floss method).
- a mechanical foaming method using a silicon surfactant which is a copolymer of polyalkylsiloxane and polyether is preferable.
- suitable silicon surfactants include SH-192 and L-5340 (manufactured by Toray Dow Corning Silicone), B8443 (manufactured by Goldschmidt), and the like.
- stabilizers such as antioxidants, lubricants, pigments, fillers, antistatic agents, and other additives may be added.
- thermosetting polyurethane foam constituting the polishing layer An example of a method for producing a thermosetting polyurethane foam constituting the polishing layer will be described below.
- the following steps (1) to (3) can be exemplified as a method for producing a cell-dispersed urethane composition that is a raw material for such a polyurethane foam.
- the first component obtained by adding a silicon-based surfactant to an isocyanate-terminated prepolymer obtained by reacting an isocyanate component and a polyol compound is mechanically stirred in the presence of a non-reactive gas to finely adjust the non-reactive gas. Disperse as bubbles to obtain a bubble dispersion. Then, a second component containing an active hydrogen-containing compound such as a low molecular weight polyol or a low molecular weight polyamine is added to the cell dispersion and mixed to prepare a cell dispersed urethane composition.
- a catalyst may be appropriately added to the second component.
- a component in which a silicon-based surfactant is added to at least one of a first component containing an isocyanate component (or an isocyanate-terminated prepolymer) and a second component containing an active hydrogen-containing compound, and a silicon-based surfactant is added Is mechanically stirred in the presence of a non-reactive gas to disperse the non-reactive gas as fine bubbles to obtain a bubble dispersion. Then, the remaining components are added to the cell dispersion and mixed to prepare a cell-dispersed urethane composition.
- a silicon-based surfactant is added to at least one of the first component containing the isocyanate component (or isocyanate-terminated prepolymer) and the second component containing the active hydrogen-containing compound, and the first component and the second component are added.
- a foam-dispersed urethane composition is prepared by mechanically stirring in the presence of a non-reactive gas and dispersing the non-reactive gas as fine bubbles.
- the cell-dispersed urethane composition may be prepared by a mechanical floss method.
- Mechanical flossing means that raw material components are put into the mixing chamber of the mixing head and non-reactive gas is mixed, and mixed and stirred with a mixer such as Oaks mixer to make the non-reactive gas into a fine bubble state in the raw material mixture. It is a method of dispersing in.
- the mechanical floss method is a preferable method because the density of the polyurethane foam can be easily adjusted by adjusting the amount of the non-reactive gas mixed therein.
- a polyurethane foam having substantially spherical fine cells having an average cell diameter of 20 to 300 ⁇ m can be continuously molded, the production efficiency is good.
- the cell-dispersed urethane composition prepared by the above method is applied onto a face material, and the cell-dispersed urethane composition is cured to form a thermosetting polyurethane foam (polishing layer) directly on the face material. .
- the non-reactive gas used for forming the fine bubbles is preferably non-flammable, and specific examples include nitrogen, oxygen, carbon dioxide gas, rare gases such as helium and argon, and mixed gases thereof.
- the use of air that has been dried to remove moisture is most preferable in terms of cost.
- a stirring device for dispersing the non-reactive gas in the form of fine bubbles a known stirring device can be used without any particular limitation. Specifically, a homogenizer, a dissolver, a two-axis planetary mixer (planetary mixer), a mechanical A floss foaming machine etc. are illustrated.
- the shape of the stirring blade of the stirring device is not particularly limited, but it is preferable to use a whipper type stirring blade because fine bubbles can be obtained.
- the stirring for preparing the cell dispersion in the foaming step and the stirring for mixing the first component and the second component use different stirring devices.
- the agitation in the mixing step may not be agitation that forms bubbles, and it is preferable to use an agitation device that does not involve large bubbles.
- a planetary mixer is suitable. There is no problem even if the same stirring device is used as the stirring device for the foaming step for preparing the bubble dispersion and the mixing step for mixing each component, and the stirring conditions such as adjusting the rotation speed of the stirring blades are adjusted as necessary. It is also suitable to use after adjustment.
- a base material layer may be laminated on the polishing layer.
- the base material layer is not particularly limited when the base material layer is laminated on the polishing layer.
- plastic films such as nylon, polypropylene, polyethylene, polyester, and polyvinyl chloride, and polymer resin foams such as polyurethane foam and polyethylene foam Bodies, rubber resins such as butadiene rubber and isoprene rubber, and photosensitive resins.
- polymer resin foams such as plastic films such as nylon, polypropylene, polyethylene, polyester, and polyvinyl chloride, polyurethane foam, and polyethylene foam.
- the base material layer preferably has a hardness equivalent to that of the polyurethane foam or harder in order to impart toughness to the polishing pad.
- the thickness of the base material layer is not particularly limited, but is preferably 20 to 1000 ⁇ m, more preferably 50 to 50 ⁇ m from the viewpoint of strength, flexibility, and the like. 800 ⁇ m.
- a roll coater such as gravure, kiss, or comma
- a die coater such as slot or phanten
- a squeeze coater or a curtain coater
- any method may be used as long as a uniform coating film can be formed on the face material.
- Heating and post-curing the polyurethane foam that has reacted until the cell-dispersed urethane composition is applied to the face material until it no longer flows has the effect of improving the physical properties of the polyurethane foam and is extremely suitable.
- Post-curing is preferably performed at 40 to 70 ° C. for 10 minutes to 24 hours, and is preferably performed at normal pressure because the bubble shape becomes stable.
- a known catalyst for promoting a polyurethane reaction such as a tertiary amine may be used.
- the type and addition amount of the catalyst are selected in consideration of the flow time for application on the face material after the mixing step of each component.
- the polyurethane foam may be produced by a batch method in which each component is weighed and put into a container and mechanically stirred, and each component and a non-reactive gas are continuously supplied to a stirring device and mechanically stirred. Further, a continuous production method in which a cell-dispersed urethane composition is sent out to produce a molded product may be used.
- the method for uniformly adjusting the thickness of the polyurethane foam is not particularly limited, and examples thereof include a method of buffing with an abrasive and a method of pressing with a press plate.
- buffing a polishing layer having no skin layer on the surface of the polyurethane foam is obtained, and when pressed, a polishing layer having a skin layer on the surface of the polyurethane foam is obtained.
- the conditions for pressing are not particularly limited, but it is preferable to adjust the temperature above the glass transition point.
- the cell-dispersed urethane composition prepared by the above method is applied onto a release sheet, and a base material layer is laminated on the cell-dispersed urethane composition. Thereafter, the polyurethane foam may be formed by curing the cell-dispersed urethane composition while making the thickness uniform by a pressing means. This method is particularly preferable because the thickness of the polishing layer can be controlled very uniformly.
- the forming material of the release sheet is not particularly limited, and examples thereof include the same resin and paper as those of the base material layer described above.
- the release sheet preferably has a small dimensional change due to heat.
- the surface of the release sheet may be subjected to a release treatment.
- the pressing means for making the thickness of the sandwich sheet composed of the release sheet, the cell-dispersed urethane composition (cell-dispersed urethane layer), and the base material layer is not particularly limited.
- the thickness may be constant by a coater roll, a nip roll, or the like.
- the method of compressing is mentioned.
- (Coating or nip clearance)-(Base layer and release sheet thickness) (After curing)
- the thickness of the polyurethane foam is preferably 50 to 85%.
- the specific gravity of the cell dispersed urethane composition before passing through the roll is preferably 0.24 to 1.
- the reacted polyurethane foam is heated and post-cured until it does not flow.
- Post cure conditions are the same as described above.
- the release sheet under the polyurethane foam is peeled off.
- a skin layer is formed on the polyurethane foam.
- the polyurethane foam is formed by the mechanical foaming method as described above, the variation in bubbles is smaller on the lower surface side than on the upper surface side of the polyurethane foam.
- the polishing surface has a small variation in bubbles, and thus the stability of the polishing rate is further improved.
- the skin layer may be removed by buffing the polyurethane foam after peeling off the release sheet.
- the thickness of the polyurethane foam is not particularly limited, but is preferably 0.2 to 3 mm, more preferably 0.5 to 2 mm.
- the polyurethane foam produced by the production method described above has substantially spherical cells.
- the polyurethane foam according to the present invention may have open cells or may have closed cells.
- the average cell diameter of the bubbles in the polyurethane foam is 20 to 300 ⁇ m, preferably 50 to 100 ⁇ m. In the case of open cells, the average diameter of the circular holes on the surface of the bubbles is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less.
- the specific gravity of the polyurethane foam is preferably 0.3 to 0.9, more preferably 0.4 to 0.5.
- the specific gravity is less than 0.3, the bubble rate becomes too high and the durability tends to deteriorate.
- the specific gravity exceeds 0.9, it is necessary to make the material have a low crosslinking density in order to obtain a certain elastic modulus. In that case, permanent set increases and durability tends to deteriorate.
- the hardness of the polyurethane foam is preferably 10 to 80 degrees in terms of Asker C hardness, and more preferably 20 to 70 degrees.
- Asker C hardness is less than 10 degrees, the durability tends to decrease or the flatness of the polished material after polishing tends to deteriorate.
- it exceeds 80 degrees scratches are likely to occur on the surface of the material to be polished.
- the shape of the polishing pad of the present invention is not particularly limited, and may be a long shape having a length of about 5 to 10 m or a round shape having a diameter of about 50 to 150 cm.
- the surface of the polishing layer may have an uneven structure for holding and renewing the slurry.
- the polishing layer made of foam has many openings on the polishing surface and has the function of holding and updating the slurry.
- the concavo-convex structure is not particularly limited as long as it is a shape that holds and renews the slurry. Examples include a cylinder, a spiral groove, an eccentric circular groove, a radial groove, and a combination of these grooves.
- these uneven structures are generally regular, but the groove pitch, groove width, groove depth, etc. can be changed for each range in order to make the slurry retention and renewability desirable. Is also possible.
- the method for producing the concavo-convex structure is not particularly limited. For example, a method of machine cutting using a tool such as a tool of a predetermined size, pouring a resin into a mold having a predetermined surface shape, and curing. Using a press plate having a predetermined surface shape, a method of producing a resin by pressing, a method of producing using photolithography, a method of producing using a printing technique, a carbon dioxide laser, etc. Examples include a manufacturing method using laser light.
- the polishing pad of the present invention may be one in which a cushion sheet is bonded to the non-polishing surface side of the polishing layer.
- a cushion sheet is bonded to the non-polishing surface side of the polishing layer.
- the cushion sheet (cushion layer) supplements the characteristics of the polishing layer.
- the cushion sheet is necessary in order to achieve both planarity and uniformity in a trade-off relationship in chemical mechanical polishing (chemical mechanical polishing).
- Planarity refers to the flatness of a pattern portion when a material having fine irregularities generated during pattern formation is polished, and uniformity refers to the uniformity of the entire material to be polished.
- the planarity is improved by the characteristics of the polishing layer, and the uniformity is improved by the characteristics of the cushion sheet.
- cushion sheet examples include fiber nonwoven fabrics such as polyester nonwoven fabric, nylon nonwoven fabric and acrylic nonwoven fabric, resin-impregnated nonwoven fabrics such as polyester nonwoven fabric impregnated with polyurethane, polymer resin foams such as polyurethane foam and polyethylene foam, butadiene rubber, and isoprene.
- fiber nonwoven fabrics such as polyester nonwoven fabric, nylon nonwoven fabric and acrylic nonwoven fabric
- resin-impregnated nonwoven fabrics such as polyester nonwoven fabric impregnated with polyurethane
- polymer resin foams such as polyurethane foam and polyethylene foam
- butadiene rubber butadiene rubber
- isoprene examples include rubber resins such as rubber and photosensitive resins.
- Examples of means for attaching the cushion sheet include a method in which a polishing layer and a cushion sheet are sandwiched with a double-sided tape and pressed.
- polishing pad of the present invention may be provided with a double-sided tape on the surface to be bonded to the platen.
- a semiconductor device is manufactured through a process of polishing the surface of a semiconductor wafer using the above-described polishing pad.
- a semiconductor wafer is generally a laminate of a wiring metal and an oxide film on a silicon wafer.
- the method and apparatus for polishing the semiconductor wafer are not particularly limited.
- a polishing surface plate 2 that supports the polishing pad 1
- a support table (polishing head) 5 that supports the semiconductor wafer 4
- This is performed using a backing material for performing uniform pressurization and a polishing apparatus equipped with a polishing agent 3 supply mechanism.
- the polishing pad 1 is attached to the polishing surface plate 2 by attaching it with a double-sided tape, for example.
- the polishing surface plate 2 and the support base 5 are disposed so that the polishing pad 1 and the semiconductor wafer 4 supported on each of the polishing surface plate 2 and the support table 5 face each other, and are provided with rotating shafts 6 and 7 respectively. Further, a pressurizing mechanism for pressing the semiconductor wafer 4 against the polishing pad 1 is provided on the support base 5 side. In polishing, the semiconductor wafer 4 is pressed against the polishing pad 1 while rotating the polishing surface plate 2 and the support base 5, and polishing is performed while supplying slurry.
- the flow rate of the slurry, the polishing load, the polishing platen rotation speed, and the wafer rotation speed are not particularly limited and are appropriately adjusted.
- a semiconductor device is manufactured by dicing, bonding, packaging, or the like.
- a semiconductor device is used for an arithmetic processing unit, a memory, and the like.
- a glass substrate for a lens or hard disk can be finished and polished by the same method as described above.
- Examples 1 to 6 and Comparative Example 1 Each raw material is put in a container so as to have a blending ratio shown in the upper part of Table 1 (the numerical value is 100 parts by weight when the total amount of polyol compound is 100 parts by weight). The mixture was vigorously stirred for about 4 minutes so as to capture bubbles. Thereafter, carbodiimide-modified MDI was added so that NCO INDEX was 1.10 and stirred for about 1 minute to prepare a cell-dispersed urethane composition.
- the prepared cell-dispersed urethane composition was applied onto a release sheet composed of a release-treated PET sheet (Toyobo Co., Ltd., thickness 75 ⁇ m) to form a cell-dispersed urethane layer. And the base material layer which consists of PET sheet
- the cell-dispersed urethane layer was made 1.5 mm thick with a nip roll, subjected to primary curing at 40 ° C. for 30 minutes, and then secondary cured at 70 ° C. for 30 minutes to form a polyurethane foam (foamed layer).
- the release sheet was peeled off.
- the thickness of the polyurethane foam was adjusted to 1.3 mm using a slicer (manufactured by Fecken) to adjust the thickness accuracy.
- a double-sided tape double tack tape, manufactured by Sekisui Chemical Co., Ltd. was bonded to the surface of the base material layer using a laminator to prepare a polishing pad.
- Polishing pad 2 Polishing surface plate 3: Abrasive (slurry) 4: Polishing target (semiconductor wafer, lens, glass plate) 5: Support base (polishing head) 6, 7: Rotating shaft
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Abstract
Description
R1-(OCH2CHR2)n-OH (1)
(式中、R1はメチル基またはエチル基であり、R2は水素原子またはメチル基であり、nは1~5の整数である)で表される化合物であることが好ましい。かかる構成を備える研磨パッドでは、研磨対象物の表面に発生する微小うねりをさらに低減することができる。
R1-(OCH2CHR2)n-OH (1)
(式中、R1はメチル基またはエチル基であり、R2は水素原子またはメチル基であり、nは1~5の整数である)で表される化合物を使用した場合、研磨対象物の表面に発生する微小うねりをさらに低減することができる。本発明にて使用可能であるモノオール化合物としては、具体的に例えば、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、2-メトキシエタノール、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノ-t-ブチルエーテル、エチレングリコールモノフェニルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノブチルエーテル、ポリエチレングリコールモノ-p-イソオクチルフェニルエーテル;酢酸、アクリル酸、メタクリル酸などのカルボン酸類のアルキレンオキサイド付加物など、が挙げられる。
JIS Z8807-1976に準拠して行った。作製したポリウレタン発泡体を4cm×8.5cmの短冊状(厚み:任意)に切り出したものをサンプルとし、温度23℃±2℃、湿度50%±5%の環境で16時間静置した。測定には比重計(ザルトリウス社製)を用い、比重を測定した。
JIS K-7312に準拠して行った。作製したポリウレタン発泡体を5cm×5cm(厚み:任意)の大きさに切り出したものをサンプルとし、温度23℃±2℃、湿度50%±5%の環境で16時間静置した。測定時には、サンプルを重ね合わせ、厚み10mm以上とした。硬度計(高分子計器社製、アスカーC型硬度計、加圧面高さ:3mm)を用い、加圧面を接触させてから30秒後の硬度を測定した。
非接触表面形状測定機(ZYGO社製NewView6300)を使用し、レンズ倍率2.5倍、ズーム倍率0.5倍で、バンドパスフィルターを200~1250μmに設定して、研磨対象物の表面5点のRaを測定し、その平均値(nm)を微小うねりとした。なお、微小うねりを測定するにあたり、以下の研磨方法で研磨した研磨対象物を使用した。
両面研磨機の設定条件
両面研磨機;スピードファム社製 9B型両面研磨機
加工圧力:100g/cm2
定盤回転数:50rpm
研磨剤供給量:4L/min
投入した基板:オハラ社製 TS-10SX
投入した基板の枚数:25枚
基板厚みが初期厚みの85%になるまで連続研磨を行った。なお、使用した研磨剤は下記の方法により調整した。
水にSHOROX A-10(昭和電工社製)を添加し、混合して、比重1.06~1.09になるように研磨剤を調整した。
使用した各原料は以下のとおりである。
(i)ポリオール化合物
ポリカプロラクトンポリオール 「プラクセル210N(PCL210N)」、官能基数:2、水酸基価:110mgKOH/g、ダイセル化学社製
ポリカプロラクトンポリオール 「プラクセル305(PCL305)」、官能基数:3、水酸基価:305mgKOH/g、ダイセル化学社製
ポリカプロラクトンポリオール 「プラクセル308(PCL308)」、官能基数:3、水酸基価:198mgKOH/g、ダイセル化学社製
ポリテトラメチレンエーテルグリコール 「PTMG1000」、官能基数:2、水酸基価:110mgKOH/g、三菱化学社製
ポリテトラメチレンエーテルグリコール 「PTMG2000」、官能基数:2、水酸基価:56mgKOH/g、三菱化学社製
ジエチレングリコール(DEG) 官能基数:2、水酸基価:1057mgKOH/g、ナカライテスク社製
1,4-ブタンジオール(1,4-BD) 官能基数:2、水酸基価:1247mgKOH/g、ナカライテスク社製
トリメチロールプロパンのプロピレンオキサイド付加体 「エクセノール890MP」、官能基数:3、水酸基価:865mgKOH/g、旭硝子社製
ジグリセリン 官能基数:4、水酸基価:1350mgKOH/g、和光純薬工業社製
(ii)モノオール化合物
ジエチレングリコールモノエチルエーテル(EtODEG) 官能基数:1、水酸基価:418mgKOH/g、ナカライテスク社製
ジエチレングリコールモノメチルエーテル(MeODEG) 官能基数:1、水酸基価:467mgKOH/g、ナカライテスク社製
(iii)触媒
「Kao No.25」、花王社製
(iv)整泡剤
「B8443」、ゴールドシュミット社製
(v)イソシアネート成分
カルボジイミド変性ジフェニルメタンジイソシアネート(MDI)、「ミリオネートMTL」、日本ポリウレタン工業社製
表1上段に記載の配合比率(数値は、ポリオール化合物全量を100重量部としたときの重量部)となるように各原料を容器に入れ、撹拌翼を用いて、回転数900rpmで反応系内に気泡を取り込むように約4分間激しく撹拌を行った。その後、カルボジイミド変性MDIを、NCO INDEXが1.10となるように添加し、約1分間撹拌して気泡分散ウレタン組成物を調製した。
2:研磨定盤
3:研磨剤(スラリー)
4:研磨対象物(半導体ウエハ、レンズ、ガラス板)
5:支持台(ポリッシングヘッド)
6、7:回転軸
Claims (9)
- 熱硬化性ポリウレタン発泡体からなる研磨層を有する研磨パッドにおいて、
前記熱硬化性ポリウレタン発泡体が、イソシアネート成分と活性水素含有化合物とを原料成分として含有し、
前記活性水素含有化合物が、官能基数が2以上であるポリオール化合物と、官能基数が1であるモノオール化合物と、を含有することを特徴とする研磨パッド。 - 前記モノオール化合物が、下記一般式(1):
R1-(OCH2CHR2)n-OH (1)
(式中、R1はメチル基またはエチル基であり、R2は水素原子またはメチル基であり、nは1~5の整数である)で表される化合物である請求項1に記載の研磨パッド。 - 前記ポリオール化合物100重量部に対して、前記モノオール化合物を1~20重量部含有する請求項1に記載の研磨パッド。
- 前記ポリオール化合物100重量部中、官能基数が3~4であり、かつ水酸基価が100~1900mgKOH/gであるポリオール化合物を20~75重量部含有する請求項1に記載の研磨パッド。
- 前記イソシアネート成分が、芳香族イソシアネートである請求項1に記載の研磨パッド。
- 前記イソシアネート成分が、カルボジイミド変性ジフェニルメタンジイソシアネートである請求項1に記載の研磨パッド。
- 前記熱硬化性ポリウレタン発泡体が、平均気泡径20~300μmの略球状の気泡を有する請求項1に記載の研磨パッド。
- 官能基数が2以上であるポリオール化合物と、官能基数が1であるモノオール化合物と、を含有する活性水素含有化合物と、イソシアネート成分と、を原料成分として含有する気泡分散ウレタン組成物を機械発泡法により調製する工程、面材上に前記気泡分散ウレタン組成物を塗布する工程、前記気泡分散ウレタン組成物を硬化させることにより、平均気泡径20~300μmの略球状の気泡を有する熱硬化性ポリウレタン発泡体からなる研磨層を形成する工程、および前記研磨層の厚さを均一に調整する工程を含む研磨パッドの製造方法。
- 請求項1に記載の研磨パッドを用いて半導体ウエハの表面を研磨する工程を含む半導体デバイスの製造方法。
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2010
- 2010-03-26 JP JP2010072948A patent/JP5528169B2/ja active Active
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2011
- 2011-03-17 KR KR1020127022940A patent/KR101399519B1/ko active IP Right Grant
- 2011-03-17 WO PCT/JP2011/056455 patent/WO2011118505A1/ja active Application Filing
- 2011-03-17 US US13/634,218 patent/US9181386B2/en active Active
- 2011-03-17 SG SG2012066114A patent/SG183939A1/en unknown
- 2011-03-17 CN CN201180011398.3A patent/CN102781627B/zh active Active
- 2011-03-23 TW TW100109873A patent/TWI450799B/zh active
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JP2006334745A (ja) * | 2005-06-03 | 2006-12-14 | Inoac Corp | 研磨用吸着パッド及びその製造方法 |
JP2010058220A (ja) * | 2008-09-03 | 2010-03-18 | Toyo Tire & Rubber Co Ltd | 研磨パッド及びその製造方法 |
JP2010064153A (ja) * | 2008-09-08 | 2010-03-25 | Kuraray Co Ltd | 研磨パッド |
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EP3892418A4 (en) * | 2018-12-03 | 2022-08-17 | Kuraray Co., Ltd. | POLYURETHANE FOR POLISHING LAYERS, POLISHING LAYER AND POLISHING PAD |
Also Published As
Publication number | Publication date |
---|---|
KR20120123129A (ko) | 2012-11-07 |
US20130035021A1 (en) | 2013-02-07 |
CN102781627A (zh) | 2012-11-14 |
SG183939A1 (en) | 2012-10-30 |
JP2011200999A (ja) | 2011-10-13 |
CN102781627B (zh) | 2015-03-11 |
KR101399519B1 (ko) | 2014-05-27 |
JP5528169B2 (ja) | 2014-06-25 |
US9181386B2 (en) | 2015-11-10 |
TW201206642A (en) | 2012-02-16 |
TWI450799B (zh) | 2014-09-01 |
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