WO2019131886A1 - 研磨パッド - Google Patents
研磨パッド Download PDFInfo
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- WO2019131886A1 WO2019131886A1 PCT/JP2018/048164 JP2018048164W WO2019131886A1 WO 2019131886 A1 WO2019131886 A1 WO 2019131886A1 JP 2018048164 W JP2018048164 W JP 2018048164W WO 2019131886 A1 WO2019131886 A1 WO 2019131886A1
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- WIPO (PCT)
- Prior art keywords
- polyurethane resin
- polishing pad
- resin foam
- polishing
- polished
- Prior art date
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- 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
- C08G18/4825—Polyethers containing two hydroxy 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
- C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
-
- 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
-
- 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
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67092—Apparatus for mechanical treatment
Definitions
- the present invention relates to a polishing pad.
- a polishing pad formed of a polyurethane resin foam is known as a polishing pad for polishing an object to be polished (glass plate or the like) (for example, Patent Document 1 etc.).
- the present invention has an object to provide a polishing pad which can improve the flatness of an object to be polished while suppressing adhesion of foreign matter to the object to be polished.
- a polishing pad according to the present invention is a polishing pad comprising a polyurethane resin foam, Has a polished surface, The polishing surface is composed of the surface of the polyurethane resin foam, The polyurethane resin foam has a tan ⁇ at 30 ° C. of 0.10 to 0.50, and an average cell diameter of 50 to 120 ⁇ m.
- the figure which shows the measurement point in the polishing pad in measurement of cutting speed The figure which shows the number of defects in a to-be-polished material when a to-be-polished material is grind
- the polishing pad according to the present embodiment is a polishing pad including a polyurethane resin foam having a polyurethane resin. Moreover, the polishing pad which concerns on this embodiment has a grinding
- the polyurethane foam preferably has a tan ⁇ at 30 ° C. of 0.10 to 0.50, preferably 0.15 to 0.40, and 0.20 to 0.40. It is more preferable that The tan ⁇ at 30 ° C. means the ratio of the loss modulus E ′ ′ at 30 ° C. to the storage modulus E ′ at 30 ° C.
- the polyurethane resin foam preferably has a storage elastic modulus E ′ at 45 ° C. of preferably 0.5 ⁇ 10 7 to 5.0 ⁇ 10 7 Pa, more preferably 1.0 ⁇ 10 7 to 4.0 ⁇ It is 10 7 Pa.
- the polyurethane resin foam preferably has a storage elastic modulus E ′ at 65 ° C. of 0.5 ⁇ 10 7 to 5.0 ⁇ 10 7 Pa, more preferably 1.0 ⁇ 10 7 to 4.0 ⁇ It is 10 7 Pa.
- storage elastic modulus E 'and loss elastic modulus E' are the following conditions according to JIS K7244-4: 1999 "Plastics-Test method of dynamic mechanical properties-Part 4: Tensile vibration-non-resonance method" It can be measured by Measurement temperature range: 0 ° C to 100 ° C Heating rate: 5 ° C / min Frequency: 1 Hz Strain: 0.5%
- the polyurethane resin foam has an average cell diameter of 50 to 120 ⁇ m.
- the standard deviation of the cell diameter of the polyurethane resin foam is preferably 10 to 55 ⁇ m.
- the average value of the bubble diameter and the standard deviation of the bubble diameter can be determined as follows using an X-ray CT scan apparatus (for example, TDM1000H-I manufactured by Yamato Scientific Co., Ltd.). That is, the volume of each cell contained in the measurement target range (for example, 0.7 mm ⁇ 1.6 mm ⁇ 1.6 mm) of the polyurethane resin foam is measured, and the diameter of a true sphere having the same volume as this volume is measured. Let the diameter of each bubble. Then, the arithmetic mean value of the diameters is obtained from the diameters of the respective bubbles, and this is made the average value of the bubble diameters. Also, the standard deviation of the diameter is determined from the diameter of each bubble, and this is taken as the standard deviation of the bubble diameter.
- TDM1000H-I manufactured by Yamato Scientific Co., Ltd.
- the cells have a circular shape in a cross section perpendicular to the polishing surface.
- the phrase "the bubbles are circular in a cross section perpendicular to the polishing surface in the polyurethane resin foam” means that "the polyurethane resin foam has a length of the bubbles represented by the following formula (1):
- the average value of the aspect ratio of is 3/5 to 5/3.
- Average value of aspect ratio of bubble length bubble length in the direction perpendicular to the polishing surface / bubble length in the direction parallel to the polishing surface (1)
- the average value of the aspect ratio of the bubble length can be determined as follows using an X-ray CT scanner (for example, TDM1000H-I manufactured by Yamato Scientific Co., Ltd.).
- a cross-sectional image of the polyurethane resin foam in a direction perpendicular to the polishing surface is taken, and 100 bubbles randomly observed in this image are selected, and for each bubble, “direction perpendicular to the polishing surface”.
- the length of the bubble and the length of the bubble in the direction parallel to the polishing surface are determined, and the aspect ratio of the bubble length is determined.
- the aspect ratio of the length of these bubbles is arithmetically averaged, and this arithmetic average value is taken as "an average value of the aspect ratios of bubble length".
- the polyurethane resin foam preferably has an apparent density of 0.4 to 0.6 g / cm 3 .
- the apparent density can be measured based on JIS K7222: 2005.
- the polyurethane resin is a second component of a first structural unit of a compound containing active hydrogen (hereinafter also referred to as “active hydrogen compound”) and a compound containing an isocyanate group (hereinafter also referred to as “isocyanate compound”). And a configuration unit.
- the polyurethane resin has a structure in which an active hydrogen compound and an isocyanate compound form a urethane bond, and a first structural unit of the active hydrogen compound and a second structural unit of the isocyanate compound are alternately repeated.
- the active hydrogen compound is an organic compound having an active hydrogen group capable of reacting with an isocyanate group in the molecule.
- Specific examples of the active hydrogen group include functional groups such as a hydroxy group, a primary amino group, a secondary amino group, and a thiol group, and the active hydrogen compound has the functional group in the molecule. It may have only one type, and may have a plurality of types of the functional group in the molecule.
- the active hydrogen compound for example, a polyol compound having a plurality of hydroxy groups in the molecule, a polyamine compound having a plurality of primary amino groups or secondary amino groups in the molecule, and the like can be used.
- polyol compound examples include polyol monomers and polyol polymers.
- polyol monomer examples include 1,4-benzenedimethanol, 1,4-bis (2-hydroxyethoxy) benzene, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1 Straight-chain aliphatic glycols such as 3,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, etc .; neopentyl Glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, etc.
- Branched aliphatic glycols, 1,4-cyclohexanediol, 1,4-cyclohexane Nord include alicyclic diols such as hydrogenated bisphenol A, glycerol, trimethylolpropane, tributylate trimethylolpropane, pentaerythritol, and the like polyfunctional polyols sorbitol and the like.
- ethylene glycol and diethylene glycol are preferable in that the reaction strength tends to be higher, the rigidity of the produced polishing pad containing the foamed polyurethane tends to be higher, and the cost is relatively low.
- polyester polyol polyester polycarbonate polyol, polyether polyol, polycarbonate polyol etc.
- polyol polymer the polyfunctional polyol polymer which has 3 or more of hydroxyl groups in a molecule
- numerator is also mentioned.
- polyester polyol examples include polyethylene adipate glycol, polybutylene adipate glycol, polycaprolactone polyol, and polyhexamethylene adipate glycol.
- polyester polycarbonate polyol examples include a reaction product of a polyester glycol such as polycaprolactone polyol and an alkylene carbonate, and a reaction mixture obtained by reacting ethylene carbonate with a polyhydric alcohol is further organic dicarboxylic acid. The reaction product reacted with is also mentioned.
- polyether polyol examples include polytetramethylene ether glycol (PTMG), polypropylene glycol (PPG), polyethylene glycol (PEG), ethylene oxide-added polypropylene polyol and the like.
- polycarbonate polyol a diol such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, or polytetramethylene ether glycol, phosgene, diallyl carbonate (For example diphenyl carbonate) or reaction products with cyclic carbonate (for example propylene carbonate) and the like.
- diol such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, or polytetramethylene ether glycol, phosgene, diallyl carbonate (For example diphenyl carbonate) or reaction products with cyclic carbonate (for example propylene carbonate) and the like.
- polyol compound examples include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol having a molecular weight of 400 or less, and the like.
- polyamine compound examples include 4,4′-methylenebis (2-chloroaniline) (MOCA), 4,4′-methylenedianiline, trimethylene bis (4-aminobenzoate), 2-methyl 4,6-bis ( (Methylthio) benzene-1,3-diamine, 2-methyl 4,6-bis (methylthio) -1,5-benzenediamine, 2,6-dichloro-p-phenylenediamine, 4,4'-methylenebis (2,3 -Dichloroaniline), 3,5-bis (methylthio) -2,4-toluenediamine, 3,5-bis (methylthio) -2,6-toluenediamine, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-2,6-diamine, trimethylene glycol-di-p-aminobenzoate, 1,2-bis (2-aminophenyne Thio) ethane, 4,4'-diamin
- polyisocyanate examples include polyisocyanate and polyisocyanate polymer.
- polyisocyanate aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate etc. are mentioned.
- aromatic diisocyanate examples include tolylene diisocyanate (TDI), 1,5-naphthalene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.
- TDI tolylene diisocyanate
- MDI diphenylmethane diisocyanate
- MDI diphenylmethane diisocyanate
- modified products of diphenylmethane diisocyanate include carbodiimide modified products, urethane modified products, allophanate modified products, urea modified products, biuret modified products, isocyanurate modified products, oxazolidone modified products and the like.
- a modified product specifically, for example, carbodiimide-modified diphenylmethane diisocyanate (carbodiimide-modified MDI) can be mentioned.
- aliphatic diisocyanates examples include ethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, hexamethylene diisocyanate (HDI) and the like.
- polyisocyanate polymer examples include polymers formed by combining a polyol and at least one of aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate.
- the polyurethane resin preferably contains polypropylene glycol (PPG) as a structural unit.
- PPG polypropylene glycol
- the polishing pad according to the present embodiment preferably contains 30% by mass or more, more preferably 40% by mass of polypropylene glycol (PPG) contained in the structural unit of the polyurethane resin, based on 100% by mass of the polyurethane resin. It is contained in an amount of up to 70% by mass, still more preferably 50 to 65% by mass.
- the content rate of the polypropylene glycol (PPG) contained in the structural unit of the said polyurethane resin in when a polyurethane resin is 100 mass% can be calculated
- a polyurethane resin foam is chemically decomposed with methanol to obtain a decomposed product.
- the decomposition product is fractionated by gel permeation chromatography (GPC) or the like and fractionated, and polypropylene glycol (PPG) is quantified by analyzing each fraction by 1 H-NMR or GC-MS. And determining the content ratio of the polypropylene glycol (PPG).
- the polishing pad according to the present embodiment is configured as described above. Next, a method of manufacturing the polishing pad according to the present embodiment will be described.
- the polishing pad which has a polyurethane resin foam is manufactured.
- distributed as air bubbles is obtained by mixing the urethane prepolymer which has an isocyanate group as an end group, and a foam-control agent.
- a polishing pad which has a polyurethane resin foam can be obtained by mixing and polymerizing a dispersion liquid and the hardening agent which is an active hydrogen organic compound which contains multiple active hydrogen in a molecule
- the foam stabilizer include silicone surfactants, fluorine surfactants, and ionic surfactants.
- polishing pad according to the present embodiment As an object to be polished by the polishing pad according to the present embodiment, an optical material, a semiconductor device, a hard disk, a glass plate, a silicon wafer, etc. may be mentioned.
- the polishing pad according to the present embodiment is suitably used for finish polishing, precision polishing, and the like.
- the polishing pad according to the present embodiment is configured as described above, and thus has the following advantages. That is, the polishing pad according to the present embodiment is a polishing pad containing a polyurethane resin foam.
- the polishing pad according to the present embodiment has a polishing surface, and the polishing surface is formed of the surface of the polyurethane resin foam.
- the polyurethane resin foam has a tan ⁇ at 30 ° C. of 0.10 to 0.50, and an average cell diameter of 50 to 120 ⁇ m. In such a polishing pad, when the tan ⁇ is large (0.10 or more), it is possible to suppress the fine vibration of the object to be polished during polishing, and to suppress the damping of the object to be polished during polishing.
- the polishing pad and the object to be polished are easily adhered.
- such a polishing pad can improve flatness.
- the average value of the cell diameter is 120 ⁇ m or less, foreign particles (grinding debris etc.) are less likely to be clogged in the bubble portion existing on the polishing surface, and as a result, the bubble portion to the object to be polished The amount of foreign matter adhering is suppressed. Therefore, according to the polishing pad which concerns on this embodiment, the flatness of to-be-polished object can be improved, suppressing adhesion of the foreign material to to-be-polished object.
- polishing pad according to the present invention is not limited to the above embodiment. Further, the polishing pad according to the present invention is not limited to the above-described effects. Furthermore, the polishing pad according to the present invention can be variously modified without departing from the scope of the present invention.
- Example 1 By mixing the prepolymer and the foam stabilizer shown in Table 1 below at a blending ratio of Table 1 below at 70 ° C., a dispersion in which air was dispersed as air bubbles was obtained. Next, the dispersion liquid and a curing agent were mixed and polymerized to obtain a polishing pad which is a polyurethane resin foam.
- Prepolymer 1 Urethane prepolymer obtained by reacting polypropylene glycol (PPG) with tolylene diisocyanate (TDI) (urethane prepolymer having an isocyanate group as an end group) (NCO wt%: 5.80) ( Takenate L1150, manufactured by Mitsui Chemicals, Inc.
- Prepolymer 2 Urethane prepolymer obtained by reacting polytetramethylene ether glycol (PTMG) with tolylene diisocyanate (TDI) (urethane prepolymer having an isocyanate group as an end group) (NCO wt%: 6.
- Prepolymer 3 Urethane prepolymer obtained by reacting polytetramethylene ether glycol (PTMG) with tolylene diisocyanate (TDI) (urethane prepolymer having an isocyanate group as an end group) (NCO wt%: 4.
- PTMG polytetramethylene ether glycol
- TDI tolylene diisocyanate
- NCO wt% 4.
- concentration of PPG of following Table 1 means the density
- Examples 2 to 4 Comparative Example 1
- a polishing pad which is a polyurethane resin foam was obtained in the same manner as in Example 1 except that materials and formulations shown in Table 1 below were used.
- the D hardness was measured in accordance with JIS K6253-1997. Specifically, a polyurethane foam cut into a size of 2 cm ⁇ 2 cm (thickness: arbitrary) is used as a sample for hardness measurement, and the sample for hardness measurement is subjected to temperature 23 ° C. ⁇ 2 ° C., humidity 50% ⁇ 5%. It left still under the environment of 16 hours.
- the thickness of the sample for hardness measurement is 6 mm or more
- the hardness of the sample for hardness measurement was measured by a hardness meter (manufactured by Kobunshi Keiki Co., Ltd., Asker D-type hardness meter).
- the thickness of the hardness measurement sample is less than 6 mm
- a plurality of hardness measurement samples are stacked in the thickness direction, and the total thickness of the stacked hardness measurement samples is 6 mm or more.
- the hardness of the sample for hardness measurement was measured by a hardness meter (manufactured by Kobunshi Keiki Co., Ltd., Asker D-type hardness meter).
- the polishing pads of Examples and Comparative Examples were processed into a donut shape as shown in FIG. 1 (outside diameter: 240 mm, inside diameter: 90 mm, thickness: about 2.0 mm), and the positions of the points shown in FIG. (12 points) A through hole having a diameter of about 3 mm was formed at this measurement point to obtain a test body.
- the test body was attached to the platen of a polishing apparatus (Ecomet 2000) via a double-sided tape, and the thickness of the test body was measured in the through hole using a depth gauge. Then, the surface of the pad was cut under the following cutting conditions.
- Pad conditioner AD3BI-100530-3 (DiaGrid ⁇ 4 inch manufactured by kinik) Condition Weight: 35g / cm 2 Platen speed: 50 rpm Head speed: 60 rpm Dressing time: 30 min Water flow rate: 100 mL / min After the cutting, the thickness of the test body was measured at the through hole using a depth gauge. Then, the cutting speed ( ⁇ m / hr) at each point is obtained from the difference in thickness of the test body before and after cutting at each point, and the arithmetic average value of the cutting speed is obtained from the cutting speed at each point. ( ⁇ m / hr).
- An object to be polished is polished under the following conditions using the polishing pads of Examples and Comparative Examples, and the object to be polished after polishing is batch-cleaned with SC-1 (wafer cleaning liquid), and then washed by sheet-fed. Then, it was dried by spin drying. After drying, the number of defects on the surface of the object to be polished and the haze level were determined.
- the defect means surface defects such as foreign matter, and the smaller the number of defects, the less foreign matter attached to the object to be polished.
- the haze means surface haze, and the smaller the haze level, the higher the flatness of the surface of the object to be polished. Further, the number of defects and the haze level were determined by the following method. In addition, for each polishing pad, ten objects to be polished were polished, and the number of defects and the haze level for each object to be polished were measured. The results are shown in FIGS.
- Object to be polished Silicon bare wafer (thickness: about 760 ⁇ m) Polishing machine: Polishing machine PNX332B, Okamoto Machine Tool Mfg. Co., Ltd. Head type: Ceramic Slurry flow rate: 600 mL / min Slurry type: RDS8-A13x31 Polishing time: 2 min Wafer pressure: 80 g / cm 2 Head speed: 29 rpm Platen speed: 30 rpm
- MAGICS Defect The number of defects (“MAGICS Defect” in FIG. 2) was measured using a wafer defect inspection / review device (MGICS M5640, manufactured by Lasertec Corporation). Only defects having a length of 190 ⁇ m or more were detected.
- ⁇ Measurement of haze level> The haze level ("Haze” in FIG. 3) was measured using a wafer surface inspection apparatus (LS6600, manufactured by Hitachi Electronics Engineering Co., Ltd.).
- the number of defects was smaller than when using the polishing pad of Comparative Example 2 in which the average value of the cell diameter was 129 ⁇ m.
- the haze level was smaller than when the polishing pad of Comparative Example 1 in which tan ⁇ at 30 ° C. was 0.079.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polishing Bodies And Polishing Tools (AREA)
Abstract
Description
研磨面を有し、
該研磨面が、前記ポリウレタン樹脂発泡体の表面で構成され、
前記ポリウレタン樹脂発泡体は、30℃でのtanδが0.10~0.50であり、気泡径の平均値が50~120μmである。
また、本実施形態に係る研磨パッドは、研磨面を有し、該研磨面が、前記ポリウレタン樹脂発泡体の表面で構成されている。
なお、30℃でのtanδは、30℃での貯蔵弾性率E’に対する30℃での損失弾性率E’’の比を意味する。
測定温度範囲:0℃~100℃
昇温速度:5℃/min
周波数:1Hz
ひずみ:0.5%
すなわち、ポリウレタン樹脂発泡体の測定対象範囲(例えば、0.7mm×1.6mm×1.6mm)に含まれている、各気泡の体積を測定し、この体積と同じ体積の真球の直径を各気泡の直径とする。
そして、各気泡の直径から直径の算術平均値を求め、これを気泡径の平均値とする。また、各気泡の直径から直径の標準偏差を求め、これを気泡径の標準偏差とする。
なお、「前記ポリウレタン樹脂発泡体では、気泡が、前記研磨面に垂直な断面において円形状となっている」とは、「前記ポリウレタン樹脂発泡体は、下記式(1)に示す気泡の長さのアスペクト比の平均値が、3/5~5/3である。」ことを意味する。
気泡の長さのアスペクト比の平均値 = 研磨面に垂直な方向の気泡の長さ/研磨面に平行した方向の気泡の長さ ・・・(1)
なお、気泡の長さのアスペクト比の平均値は、X線CTスキャン装置(例えば、ヤマト科学株式会社製のTDM1000H-I)を用いて、以下のようにして求めることができる。
すなわち、まず、研磨面に垂直な方向のポリウレタン樹脂発泡体の断面画像を撮影し、この画像において観察される気泡を無作為に100個選んで、個々の気泡について、「研磨面に垂直な方向の気泡の長さ」、及び、「研磨面に平行した方向の気泡の長さ」を求め、気泡の長さのアスペクト比を求める。
そして、これらの気泡の長さのアスペクト比を算術平均し、この算術平均値を「気泡の長さのアスペクト比の平均値」とする。
なお、断面画像の気泡の外側輪郭線上において、研磨面に垂直な方向で相互の距離が最大となる2点を選び、この2点間の距離を「研磨面に垂直な方向の気泡の長さ」とする。また、断面画像の気泡の外側輪郭線上において、研磨面に平行な方向で相互の距離が最大となる2点を選び、この2点間の距離を「研磨面に平行した方向の気泡の長さ」とする。
なお、見掛け密度は、JIS K7222:2005に基づいて測定することができる。
また、前記ポリウレタン樹脂は、活性水素化合物とイソシアネート化合物とがウレタン結合して、活性水素化合物の第1の構成単位とイソシアネート化合物の第2の構成単位とが交互に繰り返した構造となっている。
なお、ポリオールポリマーとしては、ヒドロキシ基を分子中に3以上有する多官能ポリオールポリマーも挙げられる。
また、前記ポリウレタン樹脂は、ポリプロピレングリコール(PPG)を構成単位として含むことにより、比較的もろい構造を有することになり、その結果、研磨パッドのドレス時の切削速度が高まるという利点を有する。
さらに、本実施形態に係る研磨パッドは、前記ポリウレタン樹脂を100質量%としたときに、前記ポリウレタン樹脂の構成単位に含まれるポリプロピレングリコール(PPG)を、好ましくは30質量%以上、より好ましくは40~70質量%、さらにより好ましくは50~65質量%含有する。
まず、ポリウレタン樹脂発泡体を極性溶媒(重DMF、重DMSO等)に溶かして溶解物を得る。次に、該溶解物を1H-NMRで分析することより、ポリプロピレングリコール(PPG)を定量し、前記ポリプロピレングリコール(PPG)の含有割合を求める。
また、前記ポリプロピレングリコール(PPG)の含有割合の別の求め方としては、以下の方法がある。
まず、ポリウレタン樹脂発泡体をメタノールで化学分解して分解物を得る。次に、該分解物をゲル浸透クロマトグラフィー(GPC)等で分画して分取し、各分取物を1H-NMR又はGC-MSで分析することより、ポリプロピレングリコール(PPG)を定量し、前記ポリプロピレングリコール(PPG)の含有割合を求める。
また、本実施形態に係る研磨パッドの製造方法では、末端基としてイソシアネート基を有するウレタンプレポリマーと、整泡剤とを混合することにより、空気が気泡として分散した分散液を得る。
そして、分散液と、活性水素を分子内に複数含む活性水素有機化合物たる硬化剤とを混合して重合することにより、ポリウレタン樹脂発泡体を有する研磨パッドを得ることができる。
前記整泡剤としては、シリコーン系界面活性剤、フッ素系界面活性剤、イオン性界面活性剤などが挙げられる。
また、本実施形態に係る研磨パッドは、仕上げ研磨、精密研磨等に好適に用いられる。
即ち、本実施形態に係る研磨パッドは、ポリウレタン樹脂発泡体を含む研磨パッドである。本実施形態に係る研磨パッドは、研磨面を有し、該研磨面が、前記ポリウレタン樹脂発泡体の表面で構成されている。前記ポリウレタン樹脂発泡体は、30℃でのtanδが0.10~0.50であり、気泡径の平均値が50~120μmである。
斯かる研磨パッドでは、前記tanδが大きい(0.10以上)ことにより、研磨時の被研磨物の微細振動を抑制でき、そして、研磨時の被研磨物のダンピングを抑制できる。その結果、研磨時において、研磨パッドと被研磨物とが密着しやすくなる。
その結果、斯かる研磨パッドは、平坦性を高めることができる。
また、斯かる研磨パッドでは、気泡径の平均値が120μm以下であることにより、研磨面に存在する気泡部分に異物(研磨屑等)が詰まり難くなり、その結果、気泡部分から被研磨物に付着する異物の量が抑制される。
従って、本実施形態に係る研磨パッドによれば、被研磨物への異物の付着を抑制しつつ、被研磨物の平坦性を高めることができる。
下記表1に示す、プレポリマーと、整泡剤とを下記表1の配合割合で70℃下で混合することにより、空気が気泡として分散した分散液を得た。
次に、該分散液と、硬化剤とを混合して重合することにより、ポリウレタン樹脂発泡体たる研磨パッドを得た。
・プレポリマー1:ポリプロピレングリコール(PPG)と、トリレンジイソシアネート(TDI)とを反応させることで得られるウレタンプレポリマー(末端基としてイソシアネート基を有するウレタンプレポリマー)(NCOwt%:5.80)(タケネートL1150、三井化学社製)
・プレポリマー2:ポリテトラメチレンエーテルグリコール(PTMG)と、トリレンジイソシアネート(TDI)とを反応させることで得られるウレタンプレポリマー(末端基としてイソシアネート基を有するウレタンプレポリマー)(NCOwt%:6.00)(タケネートL2695、三井化学社製)
・プレポリマー3:ポリテトラメチレンエーテルグリコール(PTMG)と、トリレンジイソシアネート(TDI)とを反応させることで得られるウレタンプレポリマー(末端基としてイソシアネート基を有するウレタンプレポリマー)(NCOwt%:4.31)(タケネートL2690、三井化学社製)
・硬化剤:MOCA(4,4’-メチレンビス(2-クロロアニリン))
・整泡剤:シリコーン系界面活性剤(デコスターブB8465、エボニック社製)
・触媒:3級アミン系触媒(トヨキャットL33、東ソー社製)
また、下記表1のPPGの濃度は、ポリウレタン樹脂を100質量%としたときに、前記ポリウレタン樹脂の構成単位に含まれるポリプロピレングリコール(PPG)の濃度を意味する。
下記表1に示す材料及び配合にしたこと以外は、実施例1と同様にして、ポリウレタン樹脂発泡体たる研磨パッドを得た。
下記表1に示す、プレポリマーと、水と、触媒とを下記表1の配合割合で70℃下で混合することにより、プレポリマーの末端基たるイソシアネート基と、水とを反応させてCO2を発生させ、CO2が気泡として分散した分散液を得た。
次に、該分散液と、硬化剤とを混合して重合することにより、ポリウレタン樹脂発泡体たる研磨パッドを得た。
D硬度は、JIS K6253-1997に準拠して測定した。
具体的には、ポリウレタン発泡体を2cm×2cm(厚み:任意)の大きさに切り出したものを硬度測定用試料とし、該硬度測定用試料を温度23℃±2℃、湿度50%±5%の環境下に16時間静置した。
ここで、硬度測定用試料の厚みが6mm以上である場合には、この硬度測定用試料の硬度を硬度計(高分子計器社製、アスカーD型硬度計)で測定した。
一方で、硬度測定用試料の厚みが6mm未満である場合には、硬度測定用試料を複数厚み方向に重ね合わせて、重ね合せた硬度測定用試料の合計の厚みを6mm以上にし、重ね合せた硬度測定用試料の硬度を硬度計(高分子計器社製、アスカーD型硬度計)で測定した。
また、見掛け密度、tanδ、及び、E’については、上述した方法で測定した。
実施例及び比較例の研磨パッドを図1に示すようなドーナツ状に加工し(外径:240mm、内径:90mm、厚み:約2.0mm)、また、図1に示す点の位置を測定ポイント(12箇所)とし、この測定ポイントにφ約3mmの貫通孔を形成して、試験体を得た。
次に、両面テープを介して研磨装置(Ecomet2000)のプラテンに前記試験体を貼り付け、デプスゲージを用いて前記貫通孔において試験体の厚みを測定した。
そして、下記切削条件でパッドの表面を切削した。
パッドコンディショナー:AD3BI-100530-3(kinik社製のDiaGridφ4inch)
コンディション
Weight:35g/cm2
プラテンスピード:50rpm
ヘッドスピード:60rpm
ドレッシング時間:30min
水の流量:100mL/min
前記切削後に、デプスゲージを用いて前記貫通孔において試験体の厚みを測定した。
そして、各ポイントの切削前後の試験体の厚みの差から、各ポイントの切削速度(μm/hr)を求め、各ポイントの切削速度から切削速度の算術平均値を求めこれを研磨パッドの切削速度(μm/hr)とした。
実施例及び比較例の研磨パッドを用い、下記条件で被研磨物を研磨し、研磨後の被研磨物をSC-1(ウエハ洗浄液)によりバッチ式で洗浄し、その後枚葉式で洗浄し、そして、スピンドライで乾燥させた。
乾燥後に、被研磨物表面におけるディフェクトの数、及び、ヘイズレベルを求めた。
なお、ディフェクトとは、異物などの表面欠陥を意味し、ディフェクトの数が小さいほど、被研磨物に付着した異物が少ないことを意味する。また、ヘイズは、表面曇りを意味し、ヘイズレベルが小さいほど、被研磨物の表面の平坦性が高いことを意味する。
また、ディフェクトの数、及び、ヘイズレベルは、以下の方法で求めた。
また、研磨パッド毎に、10枚の被研磨物を研磨し、被研磨物ごとのディフェクトの数、及び、ヘイズレベルを測定した。
結果を図2、3に示す。
被研磨物:シリコンベアウエハ(厚み:約760μm)
研磨機:ポリッシングマシンPNX332B、岡本工作機械製作所社製
ヘッドタイプ:セラミックス
スラリーの流量:600mL/min
スラリータイプ:RDS8-A13x31
研磨時間:2min
ウエハ圧力:80g/cm2
ヘッドスピード:29rpm
プラテンスピード:30rpm
ディフェクトの数(図2の「MAGICS Defect」)は、ウエハ欠陥検査/レビュー装置(MGICS M5640、レーザーテック社製)を用いて測定した。
なお、長さが190μm以上であるディフェクトのみを検出した。
ヘイズレベル(図3の「Haze」)は、ウエハ表面検査装置(LS6600、日立電子エンジニアリング株式会社製)を用いて測定した。
また、図3に示すように、実施例の研磨パッドを用いた場合、30℃でのtanδが0.079である比較例1の研磨パッドを用いた場合に比べて、ヘイズレベルが小さかった。
Claims (7)
- ポリウレタン樹脂発泡体を含む研磨パッドであって、
研磨面を有し、
該研磨面が、前記ポリウレタン樹脂発泡体の表面で構成され、
前記ポリウレタン樹脂発泡体は、30℃でのtanδが0.10~0.50であり、気泡径の平均値が50~120μmである、研磨パッド。 - 前記ポリウレタン樹脂発泡体は、気泡径の標準偏差が10~55μmである、請求項1に記載の研磨パッド。
- 前記ポリウレタン樹脂発泡体では、気泡が、前記研磨面に垂直な断面において円形状となっている、請求項1又は2に記載の研磨パッド。
- 前記ポリウレタン樹脂発泡体は、見掛け密度が0.4~0.6g/cm3である、請求項1~3の何れか1項に記載の研磨パッド。
- 前記ポリウレタン樹脂発泡体は、45℃における貯蔵弾性率E’が0.5×107~5.0×107Paである、請求項1~4の何れか1項に記載の研磨パッド。
- 前記ポリウレタン樹脂発泡体は、65℃における貯蔵弾性率E’が0.5×107~5.0×107Paである、請求項1~5の何れか1項に記載の研磨パッド。
- 前記ポリウレタン樹脂発泡体が、ポリウレタン樹脂を含有し、
前記ポリウレタン樹脂が、ポリプロピレングリコールを構成単位として含む、請求項1~6の何れか1項に記載の研磨パッド。
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