WO2021182277A1 - 研磨用組成物および研磨方法 - Google Patents
研磨用組成物および研磨方法 Download PDFInfo
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- WO2021182277A1 WO2021182277A1 PCT/JP2021/008368 JP2021008368W WO2021182277A1 WO 2021182277 A1 WO2021182277 A1 WO 2021182277A1 JP 2021008368 W JP2021008368 W JP 2021008368W WO 2021182277 A1 WO2021182277 A1 WO 2021182277A1
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- polishing
- weight
- polishing composition
- less
- abrasive grains
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- 239000011246 composite particle Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229920000359 diblock copolymer Polymers 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical group O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 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
- 229960005141 piperazine Drugs 0.000 description 1
- 229960003506 piperazine hexahydrate Drugs 0.000 description 1
- AVRVZRUEXIEGMP-UHFFFAOYSA-N piperazine;hexahydrate Chemical compound O.O.O.O.O.O.C1CNCCN1 AVRVZRUEXIEGMP-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229950004959 sorbitan oleate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- ZOMVKCHODRHQEV-UHFFFAOYSA-M tetraethylphosphanium;hydroxide Chemical compound [OH-].CC[P+](CC)(CC)CC ZOMVKCHODRHQEV-UHFFFAOYSA-M 0.000 description 1
- CRUVUWATNULHFA-UHFFFAOYSA-M tetramethylphosphanium;hydroxide Chemical compound [OH-].C[P+](C)(C)C CRUVUWATNULHFA-UHFFFAOYSA-M 0.000 description 1
- JVOPCCBEQRRLOJ-UHFFFAOYSA-M tetrapentylazanium;hydroxide Chemical compound [OH-].CCCCC[N+](CCCCC)(CCCCC)CCCCC JVOPCCBEQRRLOJ-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000000733 zeta-potential measurement Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror polishing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
Definitions
- the present invention relates to a composition for polishing a silicon wafer.
- the present invention also relates to a method for polishing a silicon wafer using the above polishing composition.
- the surface of a silicon wafer used as a component of a semiconductor device is generally finished into a high-quality mirror surface through a wrapping process (coarse polishing process) and a polishing process (precision polishing process).
- the polishing step typically includes a pre-polishing step (pre-polishing step) and a finishing polishing step (final polishing step).
- pre-polishing step pre-polishing step
- finishing polishing step final polishing step
- a polishing composition containing a water-soluble polymer is preferably used for the purpose of protecting the surface of the object to be polished and improving the wettability in addition to the abrasive grains and water.
- a polishing composition containing a water-soluble polymer is preferably used for the purpose of protecting the surface of the object to be polished and improving the wettability in addition to the abrasive grains and water.
- the polishing processability tends to decrease due to the protective action of the cellulose derivative, and it is not easy to achieve both the polishing processability and the wettability of the polished surface.
- the conventional composition containing a cellulose derivative does not always impart sufficient wettability.
- the present invention has been made in view of such circumstances, and an object of the present invention is a polishing composition capable of improving the polishing processability and the wettability of the silicon wafer surface after polishing in a composition containing a cellulose derivative. To provide things. Another object of the present invention is to provide a method for polishing a silicon wafer using such a polishing composition.
- a composition for polishing a silicon wafer contains abrasive grains, cellulose derivatives, basic compounds and water.
- the polishing composition is characterized in that the zeta potential is ⁇ 24.0 mV or more. According to the polishing composition having such a structure, the polishing rate is improved and the wettability after polishing is improved.
- a weight average molecular weight as the cellulose derivative (Mw) is larger than 80 ⁇ 10 4 is employed.
- Mw weight average molecular weight
- the zeta potential is preferably realized, and the effect of the technique disclosed herein is preferably exhibited.
- the content of the cellulose derivative is 0.1 to 20 parts by weight with respect to 100 parts by weight of the abrasive grains.
- the content of the basic compound is 0.001% by weight or more and less than 0.1% by weight. According to such a configuration, the zeta potential of the polishing composition can be easily set in a suitable range, and the polishing rate can be preferably improved.
- the pH of the polishing composition is 8.0 or more and 12.0 or less.
- the effect of improving workability by setting the zeta potential is preferably exhibited.
- silica particles are used as the abrasive grains.
- the effect of the technique disclosed herein is suitably realized in a composition containing silica particles as abrasive grains. Further, by using silica particles, contamination of the silicon wafer by components derived from abrasive particles can be prevented.
- silica particles for example, colloidal silica is preferable.
- the average primary particle size of the silica particles is 5 nm or more and 100 nm or less.
- the polishing rate improving effect can be easily obtained.
- a high-quality polished surface can be easily obtained.
- the above polishing composition is preferably used for polishing a surface made of silicon.
- the polishing composition disclosed herein can realize improvement in polishing rate and improvement in wettability in polishing a silicon wafer whose surface to be polished is made of silicon.
- the polishing composition disclosed herein is preferably used, for example, for polishing a silicon wafer that has undergone wrapping.
- a particularly preferable application target is finish polishing of a silicon wafer.
- the polishing method includes a pre-polishing step and a finish polishing step. Then, in the above-mentioned finish polishing step, the substrate to be polished is polished using a polishing composition containing abrasive grains, a cellulose derivative, a basic compound, and water and having a zeta potential of ⁇ 24.0 mV or more. It is characterized by that. According to such a polishing method, in the above-mentioned finish polishing step, the wettability of the wafer surface after polishing is improved while improving the polishing rate, and a higher quality silicon wafer surface can be obtained.
- the polishing composition disclosed herein is characterized by a zeta potential of ⁇ 24.0 mV or greater.
- the zeta potential of the polishing composition refers to the zeta potential measured by using a zeta potential measuring device for the polishing composition. More specifically, it refers to the zeta potential measured for the particles contained in the polishing composition. According to the polishing composition having a zeta potential of ⁇ 24.0 mV or more, both improvement in polishing workability and improvement in wettability of the polished surface after polishing can be achieved at the same time.
- the effect is considered to be remarkably exhibited.
- the particles in the polishing composition are likely to act on the surface of the silicon wafer which is the surface to be polished as described above, these particles are in the form of containing the abrasive grains and the cellulose derivative on the surface of the silicon wafer. It is considered that it acts on the surface, contributes to the improvement of hydrophilicity of the surface, and improves the wettability.
- the effects of the techniques disclosed herein are not limited to the above mechanisms.
- the zeta potential of the polishing composition is preferably -22.0 mV or more, more preferably -21.0 mV or more, still more preferably -20.0 mV or more, and -19.0 mV or more.
- the upper limit of the zeta potential is not particularly set, and is usually less than 0.0 mV, and -5.0 mV or less is appropriate from the viewpoint of dispersibility of the polishing composition, surface quality of the polished surface, and the like. It is preferably -10.0 mV or less, and may be, for example, -15.0 mV or less.
- the zeta potential of the polishing composition includes the type and content of abrasive grains, the type and molecular weight of the cellulose derivative, the content, and the presence or absence of other additive components (water-soluble polymers and basic compounds other than the cellulose derivative). It can be set according to the type, content, pH and the like.
- the zeta potential of the polishing composition can be measured using a known or conventional zeta potential measuring device. Specifically, it can be measured by the method described in Examples described later.
- abrasive grains contained in the polishing composition disclosed herein are not particularly limited, and can be appropriately selected depending on the purpose and mode of use of the polishing composition.
- abrasive grains include inorganic particles, organic particles, and organic-inorganic composite particles.
- the inorganic particles include oxide particles such as silica particles, alumina particles, cerium oxide particles, chromium oxide particles, titanium dioxide particles, zirconium oxide particles, magnesium oxide particles, manganese dioxide particles, zinc oxide particles, and red iron oxide particles; Nitride particles such as silicon nitride particles and boron nitride particles; carbide particles such as silicon carbide particles and boron carbide particles; diamond particles; carbonates such as calcium carbonate and barium carbonate can be mentioned.
- Specific examples of the organic particles include polymethylmethacrylate (PMMA) particles and poly (meth) acrylic acid particles (here, (meth) acrylic acid means to comprehensively refer to acrylic acid and methacrylic acid). , Polyacrylonitrile particles and the like. One type of such abrasive grains may be used alone, or two or more types may be used in combination.
- abrasive grains inorganic particles are preferable, particles made of metal or metalloid oxides are preferable, and silica particles are particularly preferable.
- a polishing composition that can be used for polishing an object to be polished (for example, finish polishing) having a surface made of silicon such as a silicon wafer, it is particularly meaningful to use silica particles as abrasive grains.
- the technique disclosed herein can be preferably carried out, for example, in a manner in which the abrasive grains are substantially composed of silica particles.
- substantially means 95% by weight or more (preferably 98% by weight or more, more preferably 99% by weight or more, and may be 100% by weight) of the particles constituting the abrasive grains. It means that it is a silica particle.
- silica particles include colloidal silica, fumed silica, precipitated silica and the like.
- the silica particles may be used alone or in combination of two or more.
- the use of colloidal silica is particularly preferable because it is easy to obtain a polished surface having excellent surface quality after polishing.
- colloidal silica for example, a colloidal silica produced from water glass (Na silicate) by an ion exchange method or an alkoxide method colloidal silica (a colloidal silica produced by a hydrolysis condensation reaction of an alkoxysilane) is preferably adopted. be able to.
- Colloidal silica can be used alone or in combination of two or more.
- the true specific gravity (true density) of the abrasive grain constituent material is preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more. .. As the true specific gravity of the abrasive grain constituent material increases, the physical polishing ability tends to increase.
- the upper limit of the true specific gravity of the abrasive grains is not particularly limited, but is typically 2.3 or less, for example 2.2 or less.
- a measured value by a liquid replacement method using ethanol as a replacement liquid can be adopted.
- the average primary particle size of the abrasive grains is not particularly limited, but is preferably 5 nm or more, more preferably 10 nm or more from the viewpoint of polishing efficiency and the like. From the viewpoint of obtaining a higher polishing effect, the average primary particle size is preferably 15 nm or more, more preferably 20 nm or more (for example, more than 20 nm). Further, from the viewpoint of suppressing the local stress applied to the surface of the object to be polished by the abrasive grains, the average primary particle size of the abrasive grains is preferably 100 nm or less, more preferably 50 nm or less, still more preferably 40 nm or less.
- the technique disclosed herein has an average primary particle size of 35 nm or less (typically less than 35 nm, more preferably 32 nm or less) because it is easy to obtain a higher quality surface (for example, a surface having a low haze level). It can also be preferably carried out in an embodiment using abrasive grains (for example, less than 30 nm).
- m 2 / g)) means the particle size (BET particle size) calculated by the formula.
- the specific surface area can be measured using, for example, a surface area measuring device manufactured by Micromeritex Co., Ltd., trade name "Flow Sorb II 2300".
- the average secondary particle size of the abrasive grains is not particularly limited, and can be appropriately selected from the range of, for example, about 15 nm to 300 nm. From the viewpoint of improving polishing efficiency, the average secondary particle size is preferably 30 nm or more, and more preferably 35 nm or more. In some embodiments, the average secondary particle size may be, for example, 40 nm or more, 45 nm or more, preferably 50 nm or more, further 60 nm or more, or 65 nm or more (for example, 70 nm or more). The average secondary particle size is usually preferably 250 nm or less, preferably 200 nm or less, and more preferably 150 nm or less. In some embodiments, the average secondary particle size may be 120 nm or less, or 100 nm or less.
- the average secondary particle size means the particle size (volume average particle size) measured by the dynamic light scattering method.
- the average secondary particle size of the abrasive grains can be measured, for example, by a dynamic light scattering method using "Nanotrack (registered trademark) UPA-UT151” manufactured by Nikkiso Co., Ltd.
- the shape (outer shape) of the abrasive grains may be spherical or non-spherical.
- the non-spherical particles include a peanut shape (that is, a peanut shell shape), a cocoon shape, a konpeito shape, a rugby ball shape, and the like.
- abrasive grains in which most of the particles are peanut-shaped or cocoon-shaped can be preferably adopted.
- the average value (average aspect ratio) of the major axis / minor axis ratio of the abrasive grains is, in principle, 1.0 or more, preferably 1.05 or more, and more preferably 1.1 or more. Is. Higher polishing efficiency can be achieved by increasing the average aspect ratio.
- the average aspect ratio of the abrasive grains is preferably 3.0 or less, more preferably 2.0 or less, still more preferably 1.5 or less, from the viewpoint of scratch reduction and the like.
- the shape (outer shape) and average aspect ratio of the abrasive grains can be grasped by, for example, observing with an electron microscope.
- an electron microscope As a specific procedure for grasping the average aspect ratio, for example, using a scanning electron microscope (SEM), each particle image of a predetermined number (for example, 200) of silica particles capable of recognizing the shape of independent particles. Draw the smallest rectangle circumscribing to. Then, for the rectangle drawn for each particle image, the value obtained by dividing the length of the long side (value of the major axis) by the length of the short side (value of the minor axis) is the major axis / minor axis ratio (aspect ratio). ).
- the average aspect ratio can be obtained by arithmetically averaging the aspect ratios of the predetermined number of particles.
- the polishing composition disclosed herein contains a cellulose derivative.
- Cellulose derivatives are polymers that contain ⁇ -glucose units as the main repeating unit.
- Specific examples of the cellulose derivative include hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose and the like. Of these, HEC is preferable.
- HEC hydroxyethyl cellulose
- one type may be used alone, or two or more types may be used in combination.
- Mw of the cellulose derivative used in the polishing composition disclosed herein is not limited to a specific range because an appropriate value can be adopted within a range in which the zeta potential of the polishing composition is equal to or higher than a predetermined value.
- Mw of the cellulose derivatives can be, for example, 30 ⁇ 10 4 or more, may also be a 50 ⁇ 10 4 or more.
- Cellulose derivatives tend to be easily adsorbed on abrasive grains (preferably silica particles), and in such cases, it is considered that the larger the Mw of the cellulose derivative, the greater the effect of reducing the electrostatic repulsion of the abrasive grains.
- abrasive grains preferably silica particles
- the upper limit of the Mw of the cellulose derivative from the viewpoint of dispersibility, it is possible to 300 ⁇ 10 4 or less, is suitably 250 ⁇ 10 4 or less, or may be 200 ⁇ 10 4 or less.
- the relationship between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose derivative is not particularly limited.
- the molecular weight distribution (Mw / Mn) of the cellulose derivative is 4.0 or more, and can be more than 5.0.
- the Mw / Mn may be 8.0 or more (for example, 9.0 or more).
- the action of the low molecular weight substance and the action of the high molecular weight substance can be expressed in a well-balanced manner.
- the Mw / Mn can be 20 or less, preferably 15 or less, and may be 12 or less, from the viewpoint of preventing the generation of agglomerates of the polishing composition and the performance stability.
- the content of the cellulose derivative in the polishing composition can be, for example, 0.01 part by weight or more per 100 parts by weight of the abrasive grains in the polishing composition, and is 0.05. It may be more than a part by weight. From the viewpoint of making better use of the effect of using the cellulose derivative, the content is preferably 0.1 part by weight or more, more preferably 1 part by weight or more, and further preferably 2 parts by weight or more.
- the content of the cellulose derivative per 100 parts by weight of the abrasive grains is usually 50 parts by weight or less, for example, 30 parts by weight or less, preferably 20 parts by weight, from the viewpoint of filterability of the polishing composition. It may be 10 parts by weight or less, 8 parts by weight or less, or 6 parts by weight or less (for example, 4 parts by weight or less).
- the polishing composition disclosed herein comprises a basic compound.
- the basic compound can be appropriately selected from various basic compounds having a function of dissolving in water and raising the pH of the aqueous solution.
- organic or inorganic basic compounds containing nitrogen, basic compounds containing phosphorus, hydroxides of alkali metals, hydroxides of alkaline earth metals, various carbonates, hydrogen carbonates and the like can be used. ..
- nitrogen-containing basic compounds include quaternary ammonium compounds, ammonia, amines (preferably water-soluble amines) and the like.
- Examples of the basic compound containing phosphorus include a quaternary phosphonium compound. Such basic compounds may be used alone or in combination of two or more.
- alkali metal hydroxides include potassium hydroxide and sodium hydroxide.
- Specific examples of carbonate or hydrogen carbonate include ammonium hydrogen carbonate, ammonium carbonate, potassium hydrogen carbonate, potassium carbonate, sodium hydrogen carbonate, sodium carbonate and the like.
- Specific examples of amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N- ( ⁇ -aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and piperazine anhydride.
- quaternary phosphonium compound include quaternary phosphonium hydroxides such as tetramethylphosphonium hydroxide and tetraethylphosphonium hydroxide.
- quaternary ammonium salt typically a strong base
- a quaternary ammonium salt such as a tetraalkylammonium salt or a hydroxyalkyltrialkylammonium salt
- Anionic component in such quaternary ammonium salts are, for example, OH -, F -, Cl -, Br -, I -, ClO 4 -, BH 4 - may be like.
- the quaternary ammonium compound include a quaternary ammonium salt having an anion of OH ⁇ , that is, a quaternary ammonium hydroxide.
- quaternary ammonium hydroxide examples include hydroxylation of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide and tetrahexylammonium hydroxide.
- the basic compound in the technique disclosed herein at least one basic compound selected from alkali metal hydroxide, quaternary ammonium hydroxide and ammonia is preferable. Of these, quaternary ammonium hydroxide and ammonia are more preferred, with ammonia particularly preferred.
- the technique disclosed herein can be preferably carried out in an embodiment in which the basic compound contained in the polishing composition is substantially composed of ammonia.
- the content of a basic compound other than ammonia is 1/10 or less (for example, 1/30 or less) of the content of ammonia on a weight basis, and is a composition for polishing.
- the zeta potential of the polishing composition is likely to be set to a predetermined value or more, and the effects of the techniques disclosed herein can be suitably exhibited.
- the content of the basic compound in the polishing composition can be, for example, 0.01 part by weight or more per 100 parts by weight of the abrasive grains in the polishing composition. It may be 05 parts by weight or more. From the viewpoint of making better use of the effect of using the basic compound, the content is preferably 0.1 part by weight or more, more preferably 0.5 part by weight or more, still more preferably 1.0 part by weight or more.
- the content of the basic compound per 100 parts by weight of the abrasive grains can be 30 parts by weight or less, preferably less than 10 parts by weight, preferably 5 parts by weight or less, and 3 parts by weight or less. May be good.
- the zeta potential of the polishing composition can be easily set to a predetermined value or more, and the polishing rate can be improved better. ..
- the content of the basic compound in the polishing composition can also be specified by the relationship between the content of abrasive grains contained in the polishing composition and the specific surface area.
- the specific surface area of abrasive grains ⁇ the content of abrasive grains / the content of basic compounds can be, for example, 1000 or more, and may be 1500 or more. From the viewpoint of making better use of the effect of using the basic compound, the above value is preferably 1750 or more, for example 2000 or more.
- the specific surface area of abrasive grains ⁇ the content of abrasive grains / the content of basic compounds can be 15,000 or less, preferably less than 12,000, preferably 11,000 or less, and 10,000 or less (for example, 8,000 or less).
- the zeta potential of the polishing composition can be easily set to a predetermined value or more, and the polishing rate can be improved better.
- the specific surface area of the abrasive grains is the specific surface area (BET value) measured by the BET method.
- the polishing composition disclosed herein may contain a water-soluble polymer (hereinafter, also referred to as an optional polymer) other than the cellulose derivative as an optional component as long as the effects of the present invention are not significantly impaired.
- a water-soluble polymer hereinafter, also referred to as an optional polymer
- an optional polymer for example, a starch derivative, a polyvinyl alcohol-based polymer, an N-vinyl type polymer, an N- (meth) acryloyl type polymer and the like can be used.
- starch derivatives include pregelatinized starch, pullulan, carboxymethyl starch, cyclodextrin and the like.
- the polyvinyl alcohol-based polymer refers to a polymer containing a vinyl alcohol unit (hereinafter, also referred to as “VA unit”) as a repeating unit thereof.
- VA unit vinyl alcohol unit
- the polyvinyl alcohol-based polymer may contain only VA units as repeating units, and may contain repeating units other than VA units (hereinafter, also referred to as “non-VA units”) in addition to VA units. Further, the polyvinyl alcohol-based polymer may be unmodified polyvinyl alcohol (non-modified PVA) or modified polyvinyl alcohol (modified PVA).
- the N-vinyl type polymer can be a homopolymer or a copolymer of the N-vinyl type monomer.
- N-vinyl type polymer examples include a homopolymer of N-vinylpyrrolidone (VP), a copolymer having a copolymerization ratio of VP of 70% by weight or more, and the like.
- the N- (meth) acryloyl type polymer can be a homopolymer or a copolymer of an N- (meth) acryloyl type monomer.
- Specific examples of the N- (meth) acryloyl type polymer include a homopolymer of N-isopropylacrylamide (NIPAM), a copolymer having a copolymerization ratio of NIPAM of 70% by weight or more, and N-acryloylmorpholin (ACMO) alone.
- NIPAM N-isopropylacrylamide
- ACMO N-acryloylmorpholin
- Examples thereof include polymers and copolymers having a copolymerization ratio of ACMO of 70% by weight or more.
- the optional polymer is preferably nonionic.
- the content of the optional polymer is usually less than 100 parts by weight, less than 50 parts by weight, less than 30 parts by weight, or less than 10 parts by weight, per 100 parts by weight of the cellulose derivative. It may be less than 5 parts by weight, or less than 1 part by weight.
- the techniques disclosed herein can be suitably carried out in a manner substantially free of such optional polymers.
- the polishing composition disclosed herein may contain a surfactant, if necessary.
- a surfactant any of anionic, cationic, nonionic and amphoteric ones can be used.
- anionic or nonionic surfactants may be preferably employed.
- Nonionic surfactants are more preferable from the viewpoint of low foaming property and ease of pH adjustment.
- oxyalkylene polymers such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, polyoxyethylene fatty acid ester, polyoxyethylene glyceryl ether fatty acid.
- Polyoxyalkylene derivatives such as esters and polyoxyethylene sorbitan fatty acid esters (eg, polyoxyalkylene adducts); copolymers of multiple oxyalkylenes (eg, diblock copolymers, triblock copolymers, etc.) Random type copolymers, alternating copolymers); and the like, nonionic surfactants can be mentioned.
- the surfactant preferably contains a surfactant containing a polyoxyalkylene structure. The surfactant may be used alone or in combination of two or more.
- nonionic surfactant containing a polyoxyalkylene structure examples include a block copolymer of ethylene oxide (EO) and propylene oxide (PO) (diblock type copolymer, PEO (polyethylene oxide) -PPO).
- EO ethylene oxide
- PO propylene oxide
- PEO polyethylene oxide
- preferred surfactants include block copolymers of EO and PO (particularly, PEO-PPO-PEO type triblock copolymers), random copolymers of EO and PO, and polyoxyethylene alkyl ethers (particularly, PEO-PPO-PEO type triblock copolymers).
- block copolymers of EO and PO particularly, PEO-PPO-PEO type triblock copolymers
- random copolymers of EO and PO random copolymers of EO and PO
- polyoxyethylene alkyl ethers particularly, PEO-PPO-PEO type triblock copolymers
- polyoxyethylene decyl ether for example, polyoxyethylene decyl ether.
- the molecular weight of the surfactant is typically less than 1 ⁇ 10 4. From the viewpoint of the filterability of the polishing composition, the detergency of the polished product, and the like, the molecular weight is preferably less than 7,000, and from the viewpoint of haze reduction, it is preferably less than 4000, more preferably less than 3500. Further, the molecular weight of the surfactant is usually preferably 200 or more from the viewpoint of surfactant ability and the like, and preferably 250 or more (for example, 300 or more) from the viewpoint of haze reducing effect and the like. A more preferable range of the molecular weight of the surfactant may also vary depending on the type of the surfactant.
- polyoxyethylene alkyl ether when used as the surfactant, its molecular weight is preferably 1500 or less, and may be 1000 or less (for example, 500 or less). Further, for example, when a PEO-PPO-PEO type triblock copolymer is used as a surfactant, its molecular weight may be, for example, 500 or more, 1000 or more, and further 2000 or more (for example, 2500). Above).
- Mw weight average molecular weight (water-based, polyethylene oxide equivalent) obtained by the above-mentioned GPC or the molecular weight calculated from the chemical formula can be adopted.
- the content of the surfactant with respect to 100 parts by weight of the abrasive grains is 20 parts by weight or less, preferably 15 parts by weight or less, and 10 parts by weight or less (for example, 6 parts by weight). (Parts or less) is more preferable.
- the content may be, for example, 5 parts by weight or less, 4 parts by weight or less, and 3 parts by weight or less with respect to 100 parts by weight of the abrasive grains.
- the content of the surfactant with respect to 100 parts by weight of the abrasive grains is preferably 0.001 part by weight or more, preferably 0.005 part by weight or more, preferably 0.01. It may be more than 0.05 parts by weight or more than 0.05 parts by weight. In some preferred embodiments, the content of the surfactant per 100 parts by weight of the abrasive grains may be 0.1 parts by weight or more from the viewpoint of haze reduction.
- the polishing composition disclosed herein can also be preferably carried out in an embodiment that is substantially free of surfactants.
- the polishing composition disclosed herein typically comprises water.
- water ion-exchanged water (deionized water), pure water, ultrapure water, distilled water and the like can be preferably used.
- the water used preferably has, for example, a total content of transition metal ions of 100 ppb or less in order to avoid hindering the action of other components contained in the polishing composition as much as possible.
- the purity of water can be increased by operations such as removal of impurity ions by an ion exchange resin, removal of foreign substances by a filter, and distillation.
- the polishing composition disclosed herein can be used for polishing of chelating agents, organic acids, organic acid salts, inorganic acids, inorganic acid salts, preservatives, fungicides, etc., as long as the effects of the present invention are not significantly impaired. If necessary, a known additive that can be used in the composition for polishing (typically, the composition for polishing a silicon wafer) may be further contained.
- the polishing composition disclosed herein can be preferably carried out in a manner substantially free of a chelating agent.
- the polishing composition disclosed herein preferably contains substantially no oxidizing agent.
- the polishing composition contains an oxidizing agent
- the polishing composition is supplied to the polishing object (silicon wafer), and the surface of the polishing object is oxidized to form an oxide film. This is because the polishing rate may decrease due to the above.
- Specific examples of the oxidizing agent referred to here include hydrogen peroxide (H 2 O 2 ), sodium persulfate, ammonium persulfate, sodium dichloroisocyanurate and the like.
- the fact that the polishing composition does not substantially contain an oxidizing agent means that the polishing composition does not contain an oxidizing agent at least intentionally.
- the pH of the polishing composition disclosed herein is usually preferably 8.0 or higher, preferably 8.5 or higher, more preferably 9.0 or higher, still more preferably 9.5 or higher. For example, it is 10.0 or more.
- the pH of the polishing composition increases, the polishing efficiency tends to improve.
- the particles containing abrasive grains and the like in the polishing composition disclosed herein tend to have a larger electrostatic repulsion as the pH is higher, and the surface of the silicon wafer to be polished tends to be negatively charged.
- Tend. According to the technique disclosed herein, by increasing the zeta potential of the polishing composition in the above pH range, the particles contained in the polishing composition can be preferably acted on the surface of the silicon wafer.
- the pH of the polishing composition is 12.0 or less. , 11.8 or less, more preferably 11.5 or less, and even more preferably 11.0 or less.
- the pH of the composition is determined by using a pH meter (for example, a glass electrode type hydrogen ion concentration indicator (model number F-23) manufactured by Horiba Seisakusho) and a standard buffer (phthalic acid).
- a pH meter for example, a glass electrode type hydrogen ion concentration indicator (model number F-23) manufactured by Horiba Seisakusho
- a standard buffer phthalic acid
- carbonate pH buffer pH: 10.01 (25 ° C) After calibrating at three points, the glass electrode is placed in the composition to be measured, and the value can be grasped by measuring the value after it has stabilized after 2 minutes or more.
- the polishing composition disclosed herein is typically supplied to an object to be polished in the form of a polishing liquid containing the composition for polishing, and is used for polishing the object to be polished.
- the polishing liquid may be prepared, for example, by diluting (typically diluting with water) any of the polishing compositions disclosed herein.
- the polishing composition may be used as it is as a polishing liquid. That is, the concept of the polishing composition in the technique disclosed herein includes a polishing liquid (working slurry) supplied to the polishing object and used for polishing the polishing object, and diluted and used as the polishing liquid. Both with the concentrate (ie, the stock solution of the polishing solution) are included.
- the polishing liquid containing the polishing composition disclosed herein there is a polishing liquid obtained by adjusting the pH of the composition.
- the content of abrasive grains in the polishing composition is not particularly limited, but is typically 0.01% by weight or more, preferably 0.05% by weight or more.
- the content may be, for example, 0.10% by weight or more, 0.20% by weight or more, 0.30% by weight or more, 0.40% by weight or more.
- Higher polishing rates can be achieved by increasing the content of abrasive grains.
- the content is preferably 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, still more preferably 2% by weight or less, for example, 1% by weight or less. It may be 5% by weight or less.
- the above-mentioned abrasive grain content can be preferably adopted in an embodiment in which the polishing composition is used in the form of a polishing liquid.
- the concentration of the cellulose derivative in the polishing composition is not particularly limited, and can be, for example, 0.0001% by weight or more, and 0.0005% by weight or more is suitable from the viewpoint of preferably exerting the effect of using the cellulose derivative. ..
- the concentration of the cellulose derivative is preferably 0.001% by weight or more, more preferably 0.002% by weight or more, for example, 0.004% by weight or more. It may be 0.008% by weight or more.
- the concentration of the cellulose derivative is usually preferably 0.2% by weight or less, more preferably 0.1% by weight or less, and 0.05% by weight or less (for example). 0.03% by weight or less) may be used.
- the above-mentioned cellulose derivative concentration can be preferably adopted in an embodiment in which the polishing composition is used in the form of a polishing liquid.
- the concentration of the basic compound in the polishing composition is not particularly limited. From the viewpoint of improving the polishing rate and the like, it is usually appropriate to set the above concentration to 0.0005% by weight or more, preferably 0.001% by weight or more, and preferably 0.005% by weight or more. More preferred. Further, from the viewpoint of haze reduction and the like, the above concentration is preferably less than 0.1% by weight, preferably less than 0.05% by weight, and less than 0.03% by weight (for example, 0.025). It is more preferable to use less than% by weight).
- the zeta potential of the polishing composition can be easily set to a predetermined value or more, and the polishing rate can be improved better.
- the above basic compound concentration can be preferably adopted in an embodiment in which the polishing composition is used in the form of a polishing liquid.
- the polishing composition disclosed herein is in a concentrated form (that is, in the form of a concentrated solution of a polishing solution, which can also be grasped as a stock solution of a polishing solution) before being supplied to an object to be polished. There may be.
- the polishing composition in such a concentrated form is advantageous from the viewpoint of convenience and cost reduction in production, distribution, storage and the like.
- the concentration ratio is not particularly limited, and can be, for example, about 2 to 100 times in terms of volume, and usually about 5 to 50 times (for example, about 10 to 40 times) is suitable.
- Such a concentrated liquid can be used in an embodiment in which a polishing liquid (working slurry) is prepared by diluting at a desired timing and the polishing liquid is supplied to an object to be polished.
- the dilution can be performed, for example, by adding water to the concentrate and mixing.
- the polishing composition used in the technique disclosed herein may be a one-dosage form or a multi-dosage form including a two-dosage form.
- part A containing at least abrasive grains among the constituents of the polishing composition and part B containing at least a part of the remaining components are mixed, and these are mixed and diluted at appropriate timings as necessary. This may be configured so that the polishing liquid is prepared.
- the method for preparing the polishing composition is not particularly limited.
- the mode in which these components are mixed is not particularly limited, and for example, all the components may be mixed at once, or may be mixed in an appropriately set order.
- the polishing composition in the technique disclosed herein can be particularly preferably used for polishing a surface made of silicon (typically polishing a silicon wafer).
- a typical example of the silicon wafer referred to here is a silicon single crystal wafer, for example, a silicon single crystal wafer obtained by slicing a silicon single crystal ingot.
- the polishing composition disclosed herein can be preferably applied to a polishing step of an object to be polished (for example, a silicon wafer).
- the object to be polished is subjected to general treatments such as lapping and etching that can be applied to the object to be polished in a process upstream of the polishing step, prior to the polishing step by the polishing composition disclosed herein. You may.
- the polishing composition disclosed herein can be preferably used, for example, in polishing a polishing object (for example, a silicon wafer) prepared to have a surface roughness of 0.01 nm to 100 nm by an upstream process.
- the surface roughness Ra of the object to be polished can be measured using, for example, a laser scan type surface roughness meter "TMS-3000WRC" manufactured by Schmitt Measurement System Inc. It is effective to use it in final polishing (finish polishing) or immediately before it, and it is particularly preferable to use it in final polishing.
- the final policing refers to the final policing step in the manufacturing process of the target product (that is, a step in which no further policing is performed after the step).
- the polishing composition disclosed herein can be used for polishing an object to be polished, for example, in an embodiment including the following operations.
- a preferred embodiment of a method of polishing an object to be polished (for example, a silicon wafer) using the polishing composition disclosed herein will be described. That is, a polishing liquid containing any of the polishing compositions disclosed herein is prepared.
- the preparation of the polishing liquid may include preparing the polishing liquid by subjecting the polishing composition to operations such as concentration adjustment (for example, dilution) and pH adjustment.
- concentration adjustment for example, dilution
- pH adjustment for example, a polishing liquid
- the polishing composition may be used as it is as a polishing liquid.
- the polishing liquid is supplied to the object to be polished and polished by a conventional method.
- the silicon wafer that has undergone the wrapping process is set in a general polishing device, and a polishing liquid is applied to the surface to be polished of the silicon wafer through the polishing pad of the polishing device.
- Supply typically, while continuously supplying the polishing liquid, the polishing pad is pressed against the surface to be polished of the silicon wafer to relatively move (for example, rotate) the two. Polishing of the object to be polished is completed through such a polishing step.
- the polishing pad used in the above polishing process is not particularly limited.
- a polishing pad such as a polyurethane foam type, a non-woven fabric type, or a suede type can be used.
- Each polishing pad may or may not contain abrasive grains.
- a polishing pad containing no abrasive grains is preferably used.
- the object to be polished which has been polished using the polishing composition disclosed herein, is typically washed. Cleaning can be performed using a suitable cleaning solution.
- the cleaning liquid used is not particularly limited, and for example, SC-1 cleaning liquid (ammonium hydroxide (NH 4 OH), hydrogen hydrogen (H 2 O 2 ), and water (H 2 O), which are common in the field of semiconductors and the like. (Mixed solution of), SC-2 cleaning solution (mixed solution of HCl, H 2 O 2 and H 2 O) and the like can be used.
- the temperature of the cleaning liquid can be, for example, in the range of room temperature (typically about 15 ° C. to 25 ° C.) or higher and up to about 90 ° C. From the viewpoint of improving the cleaning effect, a cleaning liquid having a temperature of about 50 ° C. to 85 ° C. can be preferably used.
- ⁇ Preparation of polishing composition> (Examples 1 to 3 and Comparative Example 1) Abrasive grains, cellulose derivatives, basic compounds and deionized water (DIW) were mixed to prepare a concentrated composition for polishing according to each example. Colloidal silica having an average primary particle size of 35 nm was used as the abrasive grains, hydroxyethyl cellulose (HEC) having Mw shown in Table 1 was used as the cellulose derivative, and ammonia was used as the basic compound. By diluting the obtained concentrated composition for polishing with deionized water (DIW) 20 times by volume, the concentration of abrasive grains was 0.46%, the concentration of cellulose derivative was 0.012%, and the basic compound. A polishing composition having a concentration of 0.01% was obtained.
- DIW deionized water
- ⁇ Polishing rate> (Polishing of silicon wafer)
- a silicon wafer with a diameter of 200 mm (conduction type: P type, crystal orientation: ⁇ 100>, COP (Crystal Originalized Particle: crystal defect) free) was prepared, and 30 was added to an HF aqueous solution (HF concentration: 2%). The oxide film was removed by immersing for seconds, and the polishing composition according to each example was used as a polishing liquid and polished under the following conditions.
- Polishing equipment Single-wafer polishing equipment manufactured by Okamoto Machine Tool Co., Ltd., model "PNX-322" Polishing load: 15 kPa Surface plate rotation speed: 30 rpm Head (carrier) rotation speed: 30 rpm Polishing pad: Polishing pad made by Fujibo Ehime, trade name "POLYPAS27NX” Abrasive liquid supply rate: 0.4 L / min (using flowing water) Abrasive liquid temperature: 20 ° C Polishing time: 600 seconds
- the silicon wafer was polished under the following conditions, and the surface (polished surface) of the silicon wafer was washed with running water at a flow rate of 7 L / min for 10 seconds.
- the washed wafer was allowed to stand in a state where the diagonal line of the wafer was in the vertical direction (vertical state), and the water repellency distance was measured after 3 minutes. Specifically, the length of a section of the diagonal line on the wafer surface that was not wet with water from the end of the wafer was measured, and the value was recorded as a water repellent distance [mm].
- the water-repellent distance is an index of the hydrophilicity of the polished surface, and the higher the hydrophilicity of the polished surface, the smaller the water-repellent distance tends to be.
- the maximum value of the water repellency distance in this evaluation test is the diagonal length of the wafer, that is, about 85 mm. The measurement results are shown in the corresponding columns of Table 1.
- polishing of silicon wafer A 60 mm square silicon wafer (conduction type: P type, crystal orientation: ⁇ 100>, COP free) is prepared as an object to be polished, and the oxide film is removed by immersing it in an HF aqueous solution (HF concentration: 2%) for 30 seconds. Then, the polishing composition according to each example was used as a polishing liquid and polished under the following conditions.
- Polishing device Desktop polishing machine manufactured by Nippon Engis, model "EJ-380IN” Polishing load: 21 kPa Surface plate rotation speed: 30 rpm Head (carrier) rotation speed: 30 rpm Polishing pad: Polishing pad made by Fujibo Ehime, trade name "POLYPAS27NX” Abrasive liquid supply rate: 0.6 L / min (using flowing water) Abrasive liquid temperature: 20 ° C Polishing time: 4 minutes
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Abstract
Description
ここに開示される研磨用組成物は、ゼータ電位が-24.0mV以上であることによって特徴づけられる。ここで、研磨用組成物のゼータ電位とは、研磨用組成物について、ゼータ電位測定装置を用いて測定されるゼータ電位のことをいう。より具体的には、研磨用組成物に含まれる粒子について測定されるゼータ電位をいう。ゼータ電位が-24.0mV以上である研磨用組成物によると、研磨加工性の改善と、研磨後の研磨面の濡れ性向上とを両立することができる。ここに開示される技術を実施するにあたり、研磨用組成物のゼータ電位が研磨加工性や研磨後の濡れ性向上に寄与するメカニズムを解明することは必要とされないが、以下のことが考えられる。研磨加工性に関して、負のゼータ電位を持つ研磨用組成物のゼータ電位が高くなることは、研磨用組成物において、砥粒を含む粒子の静電反発が減少することを意味し、その結果、砥粒を含む粒子は、研磨対象物に機械的に作用しやすくなり、加工性が向上するものと考えられる。特に、研磨用組成物中の粒子と同様、研磨対象物であるシリコンウェーハ表面が負電荷を持つ場合、その効果は顕著に発現するものと考えられる。また、濡れ性向上について、上記のように研磨用組成物中の粒子が研磨対象面であるシリコンウェーハ表面に作用しやすくなると、これらの粒子は、砥粒やセルロース誘導体を含む形態でシリコンウェーハ表面に作用し、当該表面の親水性向上に寄与し、濡れ性を向上させるものと考えられる。ただし、ここに開示される技術による効果は、上記のメカニズムのみに限定解釈されるものではない。
ここに開示される研磨用組成物に含まれる砥粒の材質や性状は特に制限されず、研磨用組成物の使用目的や使用態様等に応じて適宜選択することができる。砥粒の例としては、無機粒子、有機粒子、および有機無機複合粒子が挙げられる。無機粒子の具体例としては、シリカ粒子、アルミナ粒子、酸化セリウム粒子、酸化クロム粒子、二酸化チタン粒子、酸化ジルコニウム粒子、酸化マグネシウム粒子、二酸化マンガン粒子、酸化亜鉛粒子、ベンガラ粒子等の酸化物粒子;窒化ケイ素粒子、窒化ホウ素粒子等の窒化物粒子;炭化ケイ素粒子、炭化ホウ素粒子等の炭化物粒子;ダイヤモンド粒子;炭酸カルシウムや炭酸バリウム等の炭酸塩等が挙げられる。有機粒子の具体例としては、ポリメタクリル酸メチル(PMMA)粒子やポリ(メタ)アクリル酸粒子(ここで(メタ)アクリル酸とは、アクリル酸およびメタクリル酸を包括的に指す意味である。)、ポリアクリロニトリル粒子等が挙げられる。このような砥粒は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
ここに開示される研磨用組成物は、セルロース誘導体を含有する。セルロース誘導体は、主たる繰返し単位としてβ-グルコース単位を含むポリマーである。セルロース誘導体の具体例としては、ヒドロキシエチルセルロース(HEC)、ヒドロキシプロピルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロース、メチルセルロース、エチルセルロース、エチルヒドロキシエチルセルロース、カルボキシメチルセルロース等が挙げられる。なかでもHECが好ましい。セルロース誘導体は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
[GPC測定条件]
サンプル濃度:0.1重量%
カラム:TSKgel GMPWXL
検出器:示差屈折計
溶離液:100mM 硝酸ナトリウム水溶液
流速:1.0mL/分
測定温度:40℃
サンプル注入量:200μL
標準試料:ポリエチレンオキサイド
ここで開示される研磨用組成物は、塩基性化合物を含む。塩基性化合物は、水に溶解して水溶液のpHを上昇させる機能を有する各種の塩基性化合物から適宜選択され得る。例えば、窒素を含む有機または無機の塩基性化合物、リンを含む塩基性化合物、アルカリ金属の水酸化物、アルカリ土類金属の水酸化物、各種の炭酸塩や炭酸水素塩等を用いることができる。窒素を含む塩基性化合物の例としては、第四級アンモニウム化合物、アンモニア、アミン(好ましくは水溶性アミン)等が挙げられる。リンを含む塩基性化合物としては、第四級ホスホニウム化合物が挙げられる。このような塩基性化合物は、一種を単独でまたは二種以上を組み合わせて用いることができる。
ここに開示される研磨用組成物は、本発明の効果が著しく妨げられない範囲で、任意成分として、セルロース誘導体以外の水溶性高分子(以下、任意ポリマーともいう。)を含んでもよい。そのような任意ポリマーとしては、例えば、デンプン誘導体、ポリビニルアルコール系ポリマー、N-ビニル型ポリマー、N-(メタ)アクリロイル型ポリマー等が用いられ得る。デンプン誘導体の例としては、アルファ化デンプン、プルラン、カルボキシメチルデンプン、シクロデキストリン等が挙げられる。ポリビニルアルコール系ポリマーとは、その繰返し単位としてビニルアルコール単位(以下「VA単位」ともいう。)を含むポリマーを指す。ポリビニルアルコール系ポリマーは、繰返し単位としてVA単位のみを含んでいてもよく、VA単位に加えてVA単位以外の繰返し単位(以下「非VA単位」ともいう。)を含んでいてもよい。また、ポリビニルアルコール系ポリマーは、変性されていないポリビニルアルコール(非変性PVA)であってもよく、変性ポリビニルアルコール(変性PVA)であってもよい。N-ビニル型ポリマーは、N-ビニル型モノマーの単独重合体または共重合体であり得る。N-ビニル型ポリマーの具体例としては、N-ビニルピロリドン(VP)の単独重合体や、VPの共重合割合が70重量%以上の共重合体等が挙げられる。N-(メタ)アクリロイル型ポリマーは、N-(メタ)アクリロイル型モノマーの単独重合体または共重合体であり得る。N-(メタ)アクリロイル型ポリマーの具体例としては、N-イソプロピルアクリルアミド(NIPAM)の単独重合体、NIPAMの共重合割合が70重量%以上の共重合体、N-アクリロイルモルホリン(ACMO)の単独重合体、ACMOの共重合割合が70重量%以上の共重合体、等が挙げられる。任意ポリマーは、ノニオン性であることが好ましい。任意ポリマーの含有量は、セルロース誘導体100重量部当たり、通常は100重量部未満であり、50重量部未満が適当であり、30重量部未満であってもよく、10重量部未満としてもよく、5重量部未満としてもよく、1重量部未満でもよい。ここに開示される技術は、このような任意ポリマーを実質的に含有しない態様で好適に実施され得る。
ここに開示される研磨用組成物には、必要に応じて、界面活性剤を含有させることができる。研磨用組成物に界面活性剤を含有させることにより、研磨後の研磨対象物表面のヘイズをよりよく低減し得る。界面活性剤としては、アニオン性、カチオン性、ノニオン性、両性のいずれのものも使用可能である。通常は、アニオン性またはノニオン性の界面活性剤を好ましく採用し得る。低起泡性やpH調整の容易性の観点から、ノニオン性の界面活性剤がより好ましい。例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のオキシアルキレン重合体;ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレングリセリルエーテル脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等のポリオキシアルキレン誘導体(例えば、ポリオキシアルキレン付加物);複数種のオキシアルキレンの共重合体(例えば、ジブロック型共重合体、トリブロック型共重合体、ランダム型共重合体、交互共重合体);等のノニオン性界面活性剤が挙げられる。上記界面活性剤としては、ポリオキシアルキレン構造を含有する界面活性剤を含むことが好ましい。界面活性剤は、一種を単独でまたは二種以上を組み合わせて用いることができる。
ここに開示される研磨用組成物は、典型的には水を含む。水としては、イオン交換水(脱イオン水)、純水、超純水、蒸留水等を好ましく用いることができる。使用する水は、研磨用組成物に含有される他の成分の働きが阻害されることを極力回避するため、例えば遷移金属イオンの合計含有量が100ppb以下であることが好ましい。例えば、イオン交換樹脂による不純物イオンの除去、フィルタによる異物の除去、蒸留等の操作によって水の純度を高めることができる。
ここに開示される研磨用組成物は、本発明の効果が著しく妨げられない範囲で、キレート剤、有機酸、有機酸塩、無機酸、無機酸塩、防腐剤、防カビ剤等の、研磨用組成物(典型的には、シリコンウェーハ研磨用組成物)に用いられ得る公知の添加剤を、必要に応じてさらに含有してもよい。ここに開示される研磨用組成物は、キレート剤を実質的に含有しない態様で好適に実施され得る。
ここに開示される研磨用組成物のpHは、通常、8.0以上であることが適当であり、好ましくは8.5以上、より好ましくは9.0以上、さらに好ましくは9.5以上、例えば10.0以上である。研磨用組成物のpHが高くなると、研磨能率が向上する傾向にある。また、ここに開示される研磨用組成物における砥粒等を含む粒子は、pHが高いほど静電反発が大きくなる傾向があり、また研磨対象物であるシリコンウェーハ表面も負の電荷を帯びやすい傾向がある。ここに開示される技術によると、上記pH範囲にある研磨用組成物のゼータ電位を上昇させることで、研磨用組成物に含まれる粒子をシリコンウェーハ表面に好ましく作用させることができる。一方、砥粒(例えばシリカ粒子)の溶解を防ぎ、該砥粒による機械的な研磨作用の低下を抑制する観点から、研磨用組成物のpHは、12.0以下であることが適当であり、11.8以下であることが好ましく、11.5以下であることがより好ましく、11.0以下であることがさらに好ましい。
ここに開示される研磨用組成物は、典型的には該研磨用組成物を含む研磨液の形態で研磨対象物に供給されて、その研磨対象物の研磨に用いられる。上記研磨液は、例えば、ここに開示されるいずれかの研磨用組成物を希釈(典型的には、水により希釈)して調製されたものであり得る。あるいは、該研磨用組成物をそのまま研磨液として使用してもよい。すなわち、ここに開示される技術における研磨用組成物の概念には、研磨対象物に供給されて該研磨対象物の研磨に用いられる研磨液(ワーキングスラリー)と、希釈して研磨液として用いられる濃縮液(すなわち、研磨液の原液)との双方が包含される。ここに開示される研磨用組成物を含む研磨液の他の例として、該組成物のpHを調整してなる研磨液が挙げられる。
ここに開示される研磨用組成物は、研磨対象物に供給される前には濃縮された形態(すなわち、研磨液の濃縮液の形態であり、研磨液の原液としても把握され得る。)であってもよい。このように濃縮された形態の研磨用組成物は、製造、流通、保存等の際における利便性やコスト低減等の観点から有利である。濃縮倍率は特に限定されず、例えば、体積換算で2倍~100倍程度とすることができ、通常は5倍~50倍程度(例えば10倍~40倍程度)が適当である。
このような濃縮液は、所望のタイミングで希釈して研磨液(ワーキングスラリー)を調製し、該研磨液を研磨対象物に供給する態様で使用することができる。上記希釈は、例えば、上記濃縮液に水を加えて混合することにより行うことができる。
ここに開示される技術において使用される研磨用組成物は、一剤型であってもよく、二剤型を始めとする多剤型であってもよい。例えば、研磨用組成物の構成成分のうち少なくとも砥粒を含むパートAと、残りの成分の少なくとも一部を含むパートBとを混合し、これらを必要に応じて適切なタイミングで混合および希釈することにより研磨液が調製されるように構成されていてもよい。
ここに開示される技術における研磨用組成物は、シリコンからなる表面の研磨(典型的にはシリコンウェーハの研磨)に特に好ましく使用され得る。ここでいうシリコンウェーハの典型例はシリコン単結晶ウェーハであり、例えば、シリコン単結晶インゴットをスライスして得られたシリコン単結晶ウェーハである。
ここに開示される研磨用組成物は、例えば以下の操作を含む態様で、研磨対象物の研磨に使用することができる。以下、ここに開示される研磨用組成物を用いて研磨対象物(例えばシリコンウェーハ)を研磨する方法の好適な一態様につき説明する。
すなわち、ここに開示されるいずれかの研磨用組成物を含む研磨液を用意する。上記研磨液を用意することには、研磨用組成物に濃度調整(例えば希釈)、pH調整等の操作を加えて研磨液を調製することが含まれ得る。あるいは、研磨用組成物をそのまま研磨液として使用してもよい。
(実施例1~3および比較例1)
砥粒、セルロース誘導体、塩基性化合物および脱イオン水(DIW)を混合して、各例に係る研磨用組成物濃縮液を調製した。砥粒としては、平均一次粒子径が35nmのコロイダルシリカを使用し、セルロース誘導体としては、表1に示すMwを有するヒドロキシエチルセルロース(HEC)を使用し、塩基性化合物としてはアンモニアを使用した。得られた研磨用組成物濃縮液を脱イオン水(DIW)で体積比20倍に希釈することにより、砥粒の濃度を0.46%、セルロース誘導体の濃度を0.012%、塩基性化合物の濃度を0.01%とする研磨用組成物を得た。
各研磨用組成物につき、ゼータ電位測定装置を用いて下記の条件でゼータ電位を測定した。測定装置としては、Malvern社製の機種名「Zetasizer nano ZSP」を用いた。測定結果を表1の該当欄に示す。
[ゼータ電位測定条件]
分散媒:Water
測定温度:25℃
モデル:Smoluchowski
(シリコンウェーハの研磨)
研磨対象物として、直径200mmのシリコンウェーハ(伝導型:P型、結晶方位:<100>、COP(Crystal Originated Particle:結晶欠陥)フリー)を用意し、HF水溶液(HF濃度:2%)に30秒間浸漬して酸化膜を除去し、各例に係る研磨用組成物を研磨液として使用して下記の条件で研磨した。
研磨装置:株式会社岡本工作機械製作所製の枚葉研磨装置、型式「PNX-322」
研磨荷重:15kPa
定盤の回転速度:30rpm
ヘッド(キャリア)の回転速度:30rpm
研磨パッド:フジボウ愛媛社製の研磨パッド、商品名「POLYPAS27NX」
研磨液の供給レート:0.4L/分(掛け流し使用)
研磨液の温度:20℃
研磨時間:600秒
研磨後のシリコンウェーハを研磨装置から取り外し、NH4OH(29%):H2O2(31%):脱イオン水=1:1:12(体積比)の洗浄液に5分間浸漬し、洗浄した(SC-1洗浄)。その後、超音波発振器を作動した状態で脱イオン水に浸漬し、スピンドライヤーを用いて乾燥させた。
研磨前後のシリコンウェーハの重量を測定し、その重量差から、研磨レート[nm/min]を求めた。
下記条件でシリコンウェーハの研磨を実施し、シリコンウェーハの表面(研磨処理面)を流量7L/分の流水で10秒間洗浄した。洗浄後のウェーハを、該ウェーハの対角線が鉛直方向となる状態(垂直状態)で静置し、3分後に撥水距離を測定した。具体的には、ウェーハ表面における上記対角線のうち、該ウェーハの端部からの水で濡れていない区間の長さを測定し、その値を撥水距離[mm]として記録した。
なお、上記撥水距離は研磨処理面の親水性の指標であり、研磨処理面の親水性が高いほど撥水距離が小さくなる傾向にある。本評価試験における撥水距離の最大値は、上記ウェーハの対角線の長さ、すなわち約85mmである。測定結果を表1の該当欄に示す。
研磨対象物として、60mm角のシリコンウェーハ(伝導型:P型、結晶方位:<100>、COPフリー)を用意し、HF水溶液(HF濃度:2%)に30秒間浸漬して酸化膜を除去し、各例に係る研磨用組成物を研磨液として使用して下記の条件で研磨した。
研磨装置:日本エンギス社製の卓上研磨機、型式「EJ-380IN」
研磨荷重:21kPa
定盤の回転速度:30rpm
ヘッド(キャリア)の回転速度:30rpm
研磨パッド:フジボウ愛媛社製の研磨パッド、商品名「POLYPAS27NX」
研磨液の供給レート:0.6L/分(掛け流し使用)
研磨液の温度:20℃
研磨時間:4分
Claims (10)
- シリコンウェーハ研磨用組成物であって、
砥粒と、セルロース誘導体と、塩基性化合物と、水と、を含み、
前記研磨用組成物のゼータ電位は-24.0mV以上である、研磨用組成物。 - 前記セルロース誘導体の重量平均分子量は80×104よりも大きい、請求項1に記載の研磨用組成物。
- 前記セルロース誘導体の含有量は、前記砥粒100重量部に対して0.1~20重量部である、請求項1または2に記載の研磨用組成物。
- 前記塩基性化合物の含有量は0.001重量%以上0.1重量%未満である、請求項1から3のいずれか一項に記載の研磨用組成物。
- 前記研磨用組成物のpHは8.0以上12.0以下である、請求項1から4のいずれか一項に記載の研磨用組成物。
- 前記砥粒がシリカ粒子である、請求項1から5のいずれか一項に記載の研磨用組成物。
- 前記シリカ粒子の平均一次粒子径は5nm以上100nm以下である、請求項6に記載の研磨用組成物。
- シリコンからなる表面の研磨に用いられる、請求項1から7のいずれか一項に記載の研磨用組成物。
- シリコンウェーハの仕上げ研磨に用いられる、請求項1から8のいずれか一項に記載の研磨用組成物。
- シリコンウェーハを研磨する方法であって、
予備研磨工程と仕上げ研磨工程とを含み、
前記仕上げ研磨工程において、
砥粒と、セルロース誘導体と、塩基性化合物と、水と、を含み、ゼータ電位が-24.0mV以上である研磨用組成物を用いて研磨対象基板を研磨する、研磨方法。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2009290139A (ja) * | 2008-05-30 | 2009-12-10 | Sumco Techxiv株式会社 | スラリー供給装置及び同装置を用いる半導体ウェーハの研磨方法 |
JP5196819B2 (ja) | 2007-03-19 | 2013-05-15 | ニッタ・ハース株式会社 | 研磨用組成物 |
JP2020044714A (ja) | 2018-09-19 | 2020-03-26 | 大日本印刷株式会社 | 包装材料 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5196819B2 (ja) | 2007-03-19 | 2013-05-15 | ニッタ・ハース株式会社 | 研磨用組成物 |
JP2009290139A (ja) * | 2008-05-30 | 2009-12-10 | Sumco Techxiv株式会社 | スラリー供給装置及び同装置を用いる半導体ウェーハの研磨方法 |
JP2020044714A (ja) | 2018-09-19 | 2020-03-26 | 大日本印刷株式会社 | 包装材料 |
JP6761554B1 (ja) * | 2020-01-22 | 2020-09-23 | 日本酢ビ・ポバール株式会社 | 研磨用組成物 |
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