WO2015151673A1 - 研磨用組成物 - Google Patents
研磨用組成物 Download PDFInfo
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- WO2015151673A1 WO2015151673A1 PCT/JP2015/055682 JP2015055682W WO2015151673A1 WO 2015151673 A1 WO2015151673 A1 WO 2015151673A1 JP 2015055682 W JP2015055682 W JP 2015055682W WO 2015151673 A1 WO2015151673 A1 WO 2015151673A1
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- polishing
- acid
- polishing composition
- indole
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- 150000007522 mineralic acids Chemical class 0.000 description 1
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 1
- FQTCUKQMGGJRCU-UHFFFAOYSA-N n,n-diacetylacetamide Chemical compound CC(=O)N(C(C)=O)C(C)=O FQTCUKQMGGJRCU-UHFFFAOYSA-N 0.000 description 1
- UVUKMPQRNIREDM-UHFFFAOYSA-N n,n-dibenzoylbenzamide Chemical compound C=1C=CC=CC=1C(=O)N(C(=O)C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 UVUKMPQRNIREDM-UHFFFAOYSA-N 0.000 description 1
- OAXOBFOSCNGCEJ-UHFFFAOYSA-N n-[3-[[bis(2-hydroxyethyl)amino]methyl]-2,4,6-triiodophenyl]-n-(2,3-dihydroxyphenyl)acetamide;hydrochloride Chemical compound Cl.IC=1C=C(I)C(CN(CCO)CCO)=C(I)C=1N(C(=O)C)C1=CC=CC(O)=C1O OAXOBFOSCNGCEJ-UHFFFAOYSA-N 0.000 description 1
- ZHDORMMHAKXTPT-UHFFFAOYSA-N n-benzoylbenzamide Chemical compound C=1C=CC=CC=1C(=O)NC(=O)C1=CC=CC=C1 ZHDORMMHAKXTPT-UHFFFAOYSA-N 0.000 description 1
- RMHJJUOPOWPRBP-UHFFFAOYSA-N naphthalene-1-carboxamide Chemical compound C1=CC=C2C(C(=O)N)=CC=CC2=C1 RMHJJUOPOWPRBP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000003452 oxalyl group Chemical group *C(=O)C(*)=O 0.000 description 1
- 125000003355 oxamoyl group Chemical group C(C(=O)N)(=O)* 0.000 description 1
- 125000001096 oxamoylamino group Chemical group C(C(=O)N)(=O)N* 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- IHLAQQPQKRMGSS-UHFFFAOYSA-N oxiracetam Chemical compound NC(=O)CN1CC(O)CC1=O IHLAQQPQKRMGSS-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RCCYSVYHULFYHE-UHFFFAOYSA-N pentanediamide Chemical compound NC(=O)CCCC(N)=O RCCYSVYHULFYHE-UHFFFAOYSA-N 0.000 description 1
- LLYCMZGLHLKPPU-UHFFFAOYSA-N perbromic acid Chemical compound OBr(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- PYVXLMQALOZKES-UHFFFAOYSA-N periodic acid tetrabutylazanium Chemical compound C(CCC)[N+](CCCC)(CCCC)CCCC.I(=O)(=O)(=O)O PYVXLMQALOZKES-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229940094037 potassium bromate Drugs 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- LDPWMLSYNVOMKZ-UHFFFAOYSA-M potassium bromite Chemical compound [K+].[O-]Br=O LDPWMLSYNVOMKZ-UHFFFAOYSA-M 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- ORQYPOUSZINNCB-UHFFFAOYSA-N potassium;hypobromite Chemical compound [K+].Br[O-] ORQYPOUSZINNCB-UHFFFAOYSA-N 0.000 description 1
- UJQKSBYNVKHMFX-UHFFFAOYSA-N potassium;hypoiodite Chemical compound [K+].I[O-] UJQKSBYNVKHMFX-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- 150000004892 pyridazines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- UGQZLDXDWSPAOM-UHFFFAOYSA-N pyrrolo[3,4-f]isoindole-1,3,5,7-tetrone Chemical compound C1=C2C(=O)NC(=O)C2=CC2=C1C(=O)NC2=O UGQZLDXDWSPAOM-UHFFFAOYSA-N 0.000 description 1
- FPOLWERNILTNDK-UHFFFAOYSA-N pyruvamide Chemical compound CC(=O)C(N)=O FPOLWERNILTNDK-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide group Chemical group NNC(=O)N DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 239000011697 sodium iodate Substances 0.000 description 1
- 235000015281 sodium iodate Nutrition 0.000 description 1
- 229940032753 sodium iodate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NYCVSSWORUBFET-UHFFFAOYSA-M sodium;bromite Chemical compound [Na+].[O-]Br=O NYCVSSWORUBFET-UHFFFAOYSA-M 0.000 description 1
- YEBAHVHZZBYXTG-UHFFFAOYSA-N sodium;hypofluorite Chemical compound [Na+].F[O-] YEBAHVHZZBYXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N thiosemicarbazide group Chemical group NNC(=S)N BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- KHFBUINXBGUEQW-UHFFFAOYSA-N versimide Natural products COC(=O)C(=C)N1C(=O)CC(C)C1=O KHFBUINXBGUEQW-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052726 zirconium 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
-
- 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
-
- 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
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- 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
- C09G1/04—Aqueous dispersions
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
Definitions
- the present invention relates to a polishing composition.
- CMP Chemical mechanical polishing
- LSI manufacturing processes particularly in the formation of interlayer insulating films, metal plugs, and embedded wiring (damascene wiring) in the multilayer wiring forming process.
- the technology used is disclosed, for example, in US Pat. No. 4,944,836. Damascene wiring technology can simplify the wiring process and improve yield and reliability, and its application is expected to expand in the future.
- a general method of metal CMP is to apply a polishing pad on a circular polishing platen (platen), immerse the surface of the polishing pad with an abrasive and press the surface on which the metal film of the substrate is formed. In this state, the polishing platen is rotated in a state in which the pressure (hereinafter also simply referred to as polishing pressure) is applied, and the metal film on the convex portion is removed by mechanical friction between the abrasive and the convex portion of the metal film.
- polishing pressure hereinafter also simply referred to as polishing pressure
- tantalum, a tantalum alloy, a tantalum compound, or the like is formed as a barrier layer to prevent copper diffusion into the interlayer insulating film in a lower layer of copper or copper alloy of the wiring. Therefore, it is necessary to remove the exposed barrier layer by CMP except for the wiring portion in which copper or a copper alloy is embedded.
- the barrier layer is generally harder than copper or copper alloy, CMP using a combination of polishing materials for copper or copper alloy often does not provide a sufficient CMP rate.
- tantalum, tantalum alloy, or tantalum compound used as a barrier layer is chemically stable and difficult to etch, and has high hardness, so mechanical polishing is not as easy as copper or copper alloy.
- noble metal materials such as ruthenium, ruthenium alloys, and ruthenium compounds have been studied as materials for the barrier layer.
- Precious metal materials such as ruthenium, ruthenium alloys, and ruthenium compounds have a lower resistivity than tantalum, tantalum alloys, or tantalum compounds, and can be deposited by chemical vapor deposition (CVD) for thinner wiring. It is excellent in that it can be handled.
- noble metal materials such as ruthenium, ruthenium alloys, and ruthenium compounds are difficult to polish because they are chemically stable and high in hardness, like tantalum, tantalum alloys, or tantalum compounds.
- the noble metal material is used as an electrode material in a manufacturing process of a DRAM capacitor structure, for example. Then, polishing using a polishing composition is used to remove a part of a portion made of a material containing a noble metal such as ruthenium simple substance or ruthenium oxide (RuO x ).
- a noble metal such as ruthenium simple substance or ruthenium oxide (RuO x ).
- RuO x ruthenium simple substance or ruthenium oxide
- the abrasive used for CMP generally contains an oxidizing agent and abrasive grains. It is believed that the basic mechanism of CMP by this CMP abrasive is that the surface of the metal film is first oxidized by an oxidizing agent, and the resulting oxide layer on the surface of the metal film is scraped off by abrasive grains. Since the oxide layer on the surface of the metal film in the concave portion does not touch the polishing pad so much and the effect of scraping off by the abrasive grains is not exerted, the metal film on the convex portion is removed and the substrate surface is flattened with the progress of CMP.
- a high polishing rate for a wiring metal, a stable polishing rate, and a low defect density on the polishing surface are required.
- a film containing ruthenium is chemically more stable and harder than other damascene wiring metal films such as copper and tungsten, it is difficult to polish.
- Japanese Patent Application Laid-Open No. 2004-172326 proposes a polishing liquid containing abrasive grains, an oxidizing agent, and benzotriazole.
- MOSFET metal oxide semiconductor field-effect transistor
- III-V group compounds As a high mobility channel material, application of III-V group compounds, IV group compounds, graphene consisting only of Ge (germanium), C (carbon) and the like is expected. At present, the formation of III-V compound channels is easier to introduce compared to III-V compounds because there is a problem that the technology for improving the crystallinity of the channels and controlling and growing the shape is not established. Group IV compounds, particularly SiGe, Ge, and the like are being actively investigated.
- a channel using a high mobility material has a group IV compound channel and / or a Ge channel (hereinafter also referred to as a Ge material portion) and a portion containing a silicon material (hereinafter also referred to as a silicon material portion). It can be formed by polishing an object. At this time, in addition to polishing the Ge material portion at a high polishing rate, it is required that a step due to etching does not occur on the polished surface of the object to be polished. For example, in JP 2010-130009 (US Patent Application Publication No. 2010/130012) and JP 2010-519740 (US Patent Application Publication No. 2011/117740), a Ge substrate is polished. A polishing composition for use in an application is disclosed.
- JP 2010-130009 US Patent Application Publication No. 2010/130012
- JP 2010-519740 US Patent Application Publication No. 2011/117740
- an object of the present invention is to provide a polishing composition that is suitable for polishing a polishing object having a layer containing a group IV material and can prevent dissolution of the group IV material.
- the present invention is a polishing composition
- a polishing composition comprising an oxidizing agent containing a halogen atom and an organic compound containing an amide bond.
- the present invention is a polishing composition
- an oxidizing agent containing a halogen atom and an organic compound containing an amide bond.
- the polishing object according to the present invention is not particularly limited, but is suitably used for applications in which a polishing object having a layer containing a group IV material is polished. Furthermore, it is used in applications where the polishing object is polished to produce a substrate.
- the group IV material include Ge (germanium), SiGe (silicon germanium), and the like.
- the oxidizing agent used in the present invention contains a halogen atom.
- halogen acids and salts thereof chlorous acid (HClO 2 ), bromic acid (HBrO 2 ), iodic acid (HIO 2 ), sodium chlorite ( Halogenous acid or salts thereof such as NaClO 2 ), potassium chlorite (KClO 2 ), sodium bromite (NaBrO 2 ), potassium bromite (KBrO 2 ); sodium chlorate (NaClO 3 ), potassium chlorate (KClO 3 ), silver chlorate (AgClO 3 ), barium chlorate (Ba (ClO 3 ) 2 ), sodium bromate (NaBrO 3 ), potassium bromate (KBrO 3 ), sodium iodate (NaIO 3 ), etc.
- halogen acid or a salt thereof perchlorate (HClO 4), perbromic acid (HBrO 4), periodic acid (HIO 4), periodic acid isocyanatomethyl Um (NaIO 4), potassium periodate (KIO 4), periodic acid tetrabutylammonium ((C 4 H 9) 4 NIO 4) perhalogen acids or salts thereof, such as; hypofluorite (HFO), following Hypohalous acids such as chlorous acid (HClO), hypobromous acid (HBrO), hypoiodous acid (HIO); lithium hypofluorite (LiFO), sodium hypofluorite (NaFO), hypofluorite Hypochlorous acid such as potassium oxide (KFO), magnesium hypofluorite (Mg (FO) 2 ), calcium hypofluorite (Ca (FO) 2 ), and barium hypofluorite (Ba (FO) 2 ) Salt of lithium hypochlorite (LiClO), sodium hypochlorite (NaClO), potassium hypochlorite (
- chlorous acid hypochlorous acid
- chloric acid perchloric acid and salts thereof are preferable.
- salt ammonium salt, sodium salt, potassium salt and the like can be selected.
- the lower limit of the concentration of the oxidizing agent in the polishing composition of the present invention is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and 0.005% by mass or more. More preferably.
- the upper limit of the concentration of the oxidizing agent in the polishing composition of the present invention is preferably less than 0.5% by mass, more preferably 0.4% by mass or less, and 0.3% by mass or less. More preferably. If it is this range, a high grinding
- the polishing composition of the present invention contains an organic compound containing an amide bond.
- the organic compound is a compound having in its molecule an amide bond represented by —CO—NR— (the CO moiety is a double bond).
- —CO—NR— the CO moiety is a double bond.
- organic compounds include, for example, compounds having functional groups at both ends of the bond, compounds having a cyclic compound bonded to one end of the bond, and urea having functional groups at both ends as hydrogen. And urea derivatives.
- Specific examples include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, formamide, N-methylformamide, propionamide, butyramide, isobutylamide, acrylamide , Methacrylamide, palmitoamide, stearylamide, oleamide, oxamide, glutaramide, adipamide, cinnamamide, glycolamide, lactamide, glyceramide, tartaramide, citrulamide, glyoxylamide, pyruvamide, acetoacetamide, dimethylacetamide, benzylamide, anthranilamide, ethylenediamine
- R 1 is a hydrogen atom, a hydroxyl group, an aldehyde group, a carbonyl group, a carboxyl group, an amino group, an imino group, an azo group, a nitro group, a nitroso group, a thiol group, a sulfonic acid group, A phosphoric acid group, a halogen group, an alkyl group (a linear, branched or cyclic alkyl group, including a bicycloalkyl group or an active methine group), an aryl group, or an acyl group is shown. These functional groups may be unsubstituted or substituted.
- R2 represents a heterocyclic structure having 2 or more carbon atoms. These functional groups may be unsubstituted or substituted.
- the substituent is not particularly limited, and examples thereof include the following.
- Halogen atom fluorine atom, chlorine atom, bromine atom or iodine atom
- alkyl group straight chain, branched, or cyclic alkyl group including bicycloalkyl group and active methine group
- alkenyl group alkynyl group, aryl Group, heterocyclic group (any position of substitution)
- acyl group alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, N-hydroxycarbamoyl group, N-acylcarbamoyl group, N-sulfonyl Carbamoyl group, N-carbamoylcarbamoyl group, thiocarbamoyl group, N-sulfamoylcarbamoyl group, carbazoyl group, carboxy group or a salt thereof, oxalyl group, oxamoyl group, cyano group, carboximido
- the active methine group means a methine group substituted by two electron-withdrawing groups
- the electron-withdrawing group means an acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl group.
- a sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, and a carbonimidoyl group are meant.
- the two electron-withdrawing groups may be bonded to each other to form a cyclic structure.
- the salt means a cation such as alkali metal, alkaline earth metal or heavy metal, or an organic cation such as ammonium ion or phosphonium ion.
- specific examples of the compound represented by the general formula (1) include 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 5-methyl-2-pyrrolidone.
- R 3 and R 4 are each independently a hydrogen atom, a hydroxyl group, an aldehyde group, a carbonyl group, a carboxyl group, an amino group, an imino group, an azo group, a nitro group, or a nitroso group.
- These functional groups may be unsubstituted or substituted.
- n represents the number of repeating units.
- specific examples of the compound represented by the general formula (2) include poly-N-vinylacetamide.
- organic compounds containing an amide bond can be used alone or in combination of two or more.
- the lower limit of the content of the organic compound containing an amide bond in the polishing composition of the present invention is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and More preferably, it is 1% by mass or more.
- the upper limit of the content of the organic compound containing an amide bond in the polishing composition of the present invention is preferably 20% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less. More preferably. If it is this range, the effect which suppresses decomposition
- the polishing composition of the present invention preferably further contains abrasive grains.
- the abrasive has an action of mechanically polishing the object to be polished, and improves the polishing rate of the object to be polished by the polishing composition.
- the abrasive grains used in the present invention are not particularly limited, and specific examples include particles made of metal oxides such as silica, alumina, zirconia, and titania. These abrasive grains may be used alone or in combination of two or more. The abrasive grains may be commercially available products or synthetic products.
- silica is preferable, and colloidal silica is particularly preferable.
- Abrasive grains may be surface-modified. Since ordinary colloidal silica has a zeta potential value close to zero under acidic conditions, silica particles are not electrically repelled with each other under acidic conditions and are likely to agglomerate. On the other hand, abrasive grains whose surfaces are modified so that the zeta potential has a relatively large negative value even under acidic conditions are strongly repelled from each other and dispersed well even under acidic conditions, resulting in storage of the polishing composition. Stability will be improved. Such surface-modified abrasive grains can be obtained, for example, by mixing a metal such as aluminum, titanium or zirconium or an oxide thereof with the abrasive grains and doping the surface of the abrasive grains.
- a metal such as aluminum, titanium or zirconium or an oxide thereof
- colloidal silica having an organic acid immobilized thereon is particularly preferred.
- the organic acid is immobilized on the surface of the colloidal silica contained in the polishing composition, for example, by chemically bonding a functional group of the organic acid to the surface of the colloidal silica. If the colloidal silica and the organic acid are simply allowed to coexist, the organic acid is not fixed to the colloidal silica. If sulfonic acid, which is a kind of organic acid, is immobilized on colloidal silica, for example, the method described in “Sulfonic acid-functionalized silica through quantitative oxidation of thiol groups”, Chem. Commun. 246-247 (2003) It can be carried out.
- a silane coupling agent having a thiol group such as 3-mercaptopropyltrimethoxysilane is coupled to colloidal silica and then oxidized with hydrogen peroxide to fix the sulfonic acid on the surface.
- the colloidal silica thus obtained can be obtained.
- the carboxylic acid is immobilized on colloidal silica, for example, “Novel Silane Coupling Agents Containing a Photolabile 2-Nitrobenzyl Ester for Introduction of a Carboxy Group on the Surface of Silica Gel”, Chemistry Letters, 229 (2000).
- colloidal silica having a carboxylic acid immobilized on the surface can be obtained by irradiating light after coupling a silane coupling agent containing a photoreactive 2-nitrobenzyl ester to colloidal silica. .
- the lower limit of the average primary particle diameter of the abrasive grains is preferably 5 nm or more, more preferably 7 nm or more, and further preferably 10 nm or more.
- the upper limit of the average primary particle diameter of the abrasive grains is preferably 500 nm or less, more preferably 300 nm or less, and further preferably 200 nm or less.
- the polishing rate of the object to be polished by the polishing composition is improved, and the occurrence of dishing on the surface of the object to be polished after polishing with the polishing composition is further suppressed. Can do.
- the average primary particle diameter of an abrasive grain is calculated based on the specific surface area of the abrasive grain measured by BET method, for example.
- the lower limit of the content (concentration) of the abrasive grains in the polishing composition is preferably 0.0002 g / L or more, more preferably 0.002 g / L or more, and 0.02 g / L or more. More preferably it is.
- the upper limit of the content (concentration) of the abrasive grains in the polishing composition is preferably 200 g / L or less, more preferably 100 g / L or less, and further preferably 50 g / L or less. preferable. Within such a range, a high polishing rate can be obtained and processing can be performed efficiently while suppressing costs.
- the polishing composition of the present invention preferably has a pH of 5 or more, more preferably 7 or more. Moreover, the pH of the polishing composition of the present invention is preferably 12 or less, and more preferably 10 or less. If it is this range, efficient grinding
- the pH can be adjusted by adding an appropriate amount of a pH adjusting agent.
- the pH adjuster used as necessary to adjust the pH of the polishing composition to a desired value may be either acid or alkali, and may be either an inorganic compound or an organic compound. Good.
- the acid include, for example, inorganic acids such as sulfuric acid, nitric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid and phosphoric acid; formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid , N-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycol Acids, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid and lactic acid and other carboxylic acids, and methanesulf
- alkali examples include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, amines such as ammonia, ethylenediamine and piperazine, and quaternary ammonium salts such as tetramethylammonium and tetraethylammonium.
- pH regulators can be used alone or in combination of two or more.
- the polishing composition of the present invention preferably contains water as a dispersion medium or solvent for dispersing or dissolving each component. From the viewpoint of suppressing the inhibition of the action of other components, water containing as little impurities as possible is preferable. Specifically, after removing impurity ions with an ion exchange resin, pure water from which foreign matters are removed through a filter is used. Water, ultrapure water, or distilled water is preferred.
- the polishing composition of the present invention may further contain other components such as a metal anticorrosive, an antiseptic, an antifungal agent, a water-soluble polymer, and an organic solvent for dissolving a hardly soluble organic substance, as necessary. Good.
- preservative, and antifungal agent which are preferable other components are demonstrated.
- Metal anticorrosive By adding a metal anticorrosive to the polishing composition, it is possible to further suppress the formation of a dent on the side of the wiring in the polishing using the polishing composition. Moreover, it can suppress more that dishing arises on the surface of the grinding
- the metal anticorrosive that can be used is not particularly limited, but is preferably a heterocyclic compound or a surfactant.
- the number of heterocyclic rings in the heterocyclic compound is not particularly limited.
- the heterocyclic compound may be a monocyclic compound or a polycyclic compound having a condensed ring.
- These metal anticorrosives may be used alone or in combination of two or more.
- a commercially available product or a synthetic product may be used as the metal anticorrosive.
- isoindole compound indazole compound, purine compound, quinolidine compound, quinoline compound, isoquinoline compound, naphthyridine compound, phthalazine compound, quinoxaline compound, quinazoline compound, cinnoline compound, buteridine compound, thiazole compound, isothiazole compound, oxazole compound, iso Examples thereof include nitrogen-containing heterocyclic compounds such as oxazole compounds and furazane compounds.
- More specific examples include pyrazole compounds such as 1H-pyrazole, 4-nitro-3-pyrazolecarboxylic acid, 3,5-pyrazolecarboxylic acid, 3-amino-5-phenylpyrazole, 5 -Amino-3-phenylpyrazole, 3,4,5-tribromopyrazole, 3-aminopyrazole, 3,5-dimethylpyrazole, 3,5-dimethyl-1-hydroxymethylpyrazole, 3-methylpyrazole, 1-methyl Pyrazole, 3-amino-5-methylpyrazole, 4-amino-pyrazolo [3,4-d] pyrimidine, allopurinol, 4-chloro-1H-pyrazolo [3,4-D] pyrimidine, 3,4-dihydroxy-6 -Methylpyrazolo (3,4-B) -pyridine, 6-methyl-1H-pyrazolo [3,4-b] pyridine 3-amine, and the like.
- pyrazole compounds such as 1H-pyrazole, 4-
- imidazole compounds include imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1,2-dimethylpyrazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, benzimidazole, 5,6-dimethylbenzimidazole, 2-aminobenzimidazole, 2-chlorobenzimidazole, 2-methylbenzimidazole, 2- (1-hydroxyethyl) benzimidazole, 2-hydroxybenzimidazole, 2-phenylbenzimidazole, 2 , 5-dimethylbenzimidazole, 5-methylbenzimidazole, 5-nitrobenzimidazole, 1H-purine and the like.
- triazole compounds include, for example, 1,2,3-triazole, 1,2,4-triazole, 1-methyl-1,2,4-triazole, methyl-1H-1,2,4-triazole-3 -Carboxylate, 1,2,4-triazole-3-carboxylic acid, methyl 1,2,4-triazole-3-carboxylate, 1H-1,2,4-triazole-3-thiol, 3,5-diamino -1H-1,2,4-triazole, 3-amino-1,2,4-triazole-5-thiol, 3-amino-1H-1,2,4-triazole, 3-amino-5-benzyl-4H -1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 3-nitro-1,2,4-triazole, 3-bromo-5-nitro-1,2 , 4-to Azole, 4- (1,2,4-triazol-1-yl) phenol, 4-amino-1,2,4-triazole,
- tetrazole compounds include 1H-tetrazole, 5-methyltetrazole, 5-aminotetrazole, 5-phenyltetrazole, and the like.
- indazole compounds include, for example, 1H-indazole, 5-amino-1H-indazole, 5-nitro-1H-indazole, 5-hydroxy-1H-indazole, 6-amino-1H-indazole, 6-nitro-1H -Indazole, 6-hydroxy-1H-indazole, 3-carboxy-5-methyl-1H-indazole and the like.
- indole compounds include, for example, 1H-indole, 1-methyl-1H-indole, 2-methyl-1H-indole, 3-methyl-1H-indole, 4-methyl-1H-indole, 5-methyl-1H- Indole, 6-methyl-1H-indole, 7-methyl-1H-indole, 4-amino-1H-indole, 5-amino-1H-indole, 6-amino-1H-indole, 7-amino-1H-indole, 4-hydroxy-1H-indole, 5-hydroxy-1H-indole, 6-hydroxy-1H-indole, 7-hydroxy-1H-indole, 4-methoxy-1H-indole, 5-methoxy-1H-indole, 6- Methoxy-1H-indole, 7-methoxy-1H-indole, 4-chloro-1H Indole, 5-chloro-1H-indole, 6-chloro-1H Indo
- heterocyclic compounds are triazole compounds, and in particular, 1H-benzotriazole, 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, 1- [N, N-bis (hydroxy Ethyl) aminomethyl] -5-methylbenzotriazole, 1- [N, N-bis (hydroxyethyl) aminomethyl] -4-methylbenzotriazole, 1,2,3-triazole, and 1,2,4-triazole Is preferred. Since these heterocyclic compounds have high chemical or physical adsorptive power to the surface of the object to be polished, a stronger protective film can be formed on the surface of the object to be polished. This is advantageous in improving the flatness of the surface of the object to be polished after polishing using the polishing composition of the present invention.
- the surfactant used as the metal anticorrosive may be any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.
- anionic surfactants include, for example, polyoxyethylene alkyl ether acetic acid, polyoxyethylene alkyl sulfuric acid ester, alkyl sulfuric acid ester, polyoxyethylene alkyl ether sulfuric acid, alkyl ether sulfuric acid, alkylbenzene sulfonic acid, alkyl phosphoric acid ester , Polyoxyethylene alkyl phosphate ester, polyoxyethylene sulfosuccinic acid, alkyl sulfosuccinic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, and salts thereof.
- Examples of the cationic surfactant include alkyl trimethyl ammonium salt, alkyl dimethyl ammonium salt, alkyl benzyl dimethyl ammonium salt, alkyl amine salt and the like.
- amphoteric surfactants include alkyl betaines and alkyl amine oxides.
- nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and alkyl alkanolamide. Is mentioned.
- preferable surfactants are polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl ether sulfate, alkyl ether sulfate, alkylbenzene sulfonate, and polyoxyethylene alkyl ether. Since these surfactants have a high chemical or physical adsorption force to the surface of the object to be polished, a stronger protective film can be formed on the surface of the object to be polished. This is advantageous in improving the flatness of the surface of the object to be polished after polishing using the polishing composition of the present invention.
- antiseptics and fungicides examples include isothiazoline-based antiseptics such as 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, Paraoxybenzoates, phenoxyethanol and the like can be mentioned. These antiseptics and fungicides may be used alone or in combination of two or more.
- the production method of the polishing composition of the present invention is not particularly limited, and for example, an oxidizing agent containing a halogen atom and an organic compound containing an amide bond, and other components as necessary are stirred and mixed in water. Can be obtained.
- the temperature at the time of mixing each component is not particularly limited, but is preferably 10 to 40 ° C., and may be heated to increase the dissolution rate. Further, the mixing time is not particularly limited.
- the polishing composition of the present invention is particularly suitably used for polishing a polishing object having a layer containing a group IV material. Therefore, this invention provides the grinding
- a polishing apparatus As a polishing apparatus, a general holder having a polishing surface plate on which a holder for holding a substrate having a polishing object and a motor capable of changing the number of rotations are attached and a polishing pad (polishing cloth) can be attached A polishing apparatus can be used.
- polishing pad a general nonwoven fabric, polyurethane, porous fluororesin, or the like can be used without particular limitation. It is preferable that the polishing pad is grooved so that the polishing liquid accumulates.
- the polishing conditions are not particularly limited.
- the rotation speed of the polishing platen is preferably 10 to 500 rpm, and the pressure applied to the substrate having the object to be polished (polishing pressure) is preferably 0.5 to 10 psi.
- the method of supplying the polishing composition to the polishing pad is not particularly limited, and for example, a method of continuously supplying with a pump or the like is employed. Although the supply amount is not limited, it is preferable that the surface of the polishing pad is always covered with the polishing composition of the present invention.
- the substrate After completion of polishing, the substrate is washed in running water, and water droplets adhering to the substrate are removed by drying with a spin dryer or the like, and dried to obtain a substrate having a layer containing a group IV material.
- Examples 1 to 9, Comparative Examples 1 to 29 The organic compound containing the amide bond shown in Table 1 was added so that it might become content in the composition shown in Table 1. Further, an aqueous solution of sodium hypochlorite (concentration: 5.9% by mass) or a hydrogen peroxide aqueous solution (concentration: 31% by mass) as an oxidant is 0.03% by mass as the content in the composition. The mixture was stirred and mixed in water (mixing temperature: about 25 ° C., mixing time: about 10 minutes) to prepare polishing compositions of Examples 1 to 9 and Comparative Examples 1 to 29. The pH of the polishing composition was adjusted by adding potassium hydroxide (KOH) and confirmed with a pH meter.
- KOH potassium hydroxide
- the ratio of the remaining oxidant was announced by the Ministry of Health, Labor and Welfare on September 29, 2003 between the polishing composition before storage and the polishing composition after storage at 25 ° C. for 7 days.
- the content of the oxidizing agent was measured by the method of No. 318, and calculated by the following formula.
- Ratio of remaining oxidizing agent (%) (Amount of oxidizing agent in polishing composition after storage) / (Amount of oxidizing agent in polishing composition before storage) ⁇ 100
- the etching rate of the Ge substrate is the immersion condition: a Ge substrate of 3 cm ⁇ 3 cm is immersed for 5 minutes at 43 ° C. (while the stirrer is rotated at 300 rpm), and the amount of dissolution is calculated from the subsequent weight change. was divided by the immersion time, and the etching rate of the Ge substrate was measured.
- Table 1 shows the compositions of the polishing compositions of Examples 1 to 9 and Comparative Examples 1 to 29, and the measurement results of the Ge etching rate and the oxidant residue rate.
- polishing compositions of Examples 1 to 9 suppressed the dissolution of Ge.
- the polishing compositions of Comparative Examples 2 to 3 and Comparative Examples 8 to 13 the Ge etching rate is low, but the oxidant residue ratio is low, and these polishing compositions decompose the oxidant. I understand that.
- Examples 10 to 19, Comparative Examples 30 to 46 Colloidal silica having an average primary particle diameter of 30 nm and an average secondary particle diameter of 62 nm as abrasive grains, NaClO as a halogen-containing oxidizing agent, and compounds shown in Table 3 below as organic compounds containing an amide group, With the contents shown in Table 3, the mixture was stirred and mixed in water (mixing temperature: about 25 ° C., mixing time: about 10 minutes) to prepare the polishing compositions of Examples 10 to 19 and Comparative Examples 30 to 46. . The pH of the polishing composition was adjusted to pH 8.5 by adding nitric acid (HNO 3 ) or potassium hydroxide (KOH).
- HNO 3 nitric acid
- KOH potassium hydroxide
- the polishing rate was determined when the polishing compositions of Examples 10 to 19 and Comparative Examples 30 to 46 were polished for a predetermined time under the polishing conditions shown in Table 2 below.
- a Ge substrate crystal orientation (100) was used as a coupon of 3 cm ⁇ 3 cm.
- the polishing rate of the Ge substrate was determined from the difference in weight before and after polishing.
- the polishing rate of the TEOS substrate was determined by dividing the difference in film thickness before and after polishing measured by using an optical interference film thickness measuring apparatus by the polishing time.
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Abstract
Description
本発明に係る研磨対象物は、特に制限されないが、IV族材料を含む層を有する研磨対象物を研磨する用途に好適に用いられる。さらに言えば、その研磨対象物を研磨して基板を製造する用途で使用される。IV族材料の例としては、Ge(ゲルマニウム)、SiGe(シリコンゲルマニウム)等が挙げられる。
本発明で用いられる酸化剤は、ハロゲン原子を含有する。かような酸化剤の具体的な例としては、例えば、ハロゲン酸およびその塩、亜塩素酸(HClO2)、亜臭素酸(HBrO2)、亜ヨウ素酸(HIO2)、亜塩素酸ナトリウム(NaClO2)、亜塩素酸カリウム(KClO2)、亜臭素酸ナトリウム(NaBrO2)、亜臭素酸カリウム(KBrO2)等の亜ハロゲン酸またはその塩;塩素酸ナトリウム(NaClO3)、塩素酸カリウム(KClO3)、塩素酸銀(AgClO3)、塩素酸バリウム(Ba(ClO3)2)、臭素酸ナトリウム(NaBrO3)、臭素酸カリウム(KBrO3)、ヨウ素酸ナトリウム(NaIO3)等のハロゲン酸またはその塩;過塩素酸(HClO4)、過臭素酸(HBrO4)、過ヨウ素酸(HIO4)、過ヨウ素酸ナトリウム(NaIO4)、過ヨウ素酸カリウム(KIO4)、過ヨウ素酸テトラブチルアンモニウム((C4H9)4NIO4)等の過ハロゲン酸またはその塩;次亜フッ素酸(HFO)、次亜塩素酸(HClO)、次亜臭素酸(HBrO)、次亜ヨウ素酸(HIO)等の次亜ハロゲン酸;次亜フッ素酸リチウム(LiFO)、次亜フッ素酸ナトリウム(NaFO)、次亜フッ素酸カリウム(KFO)、次亜フッ素酸マグネシウム(Mg(FO)2)、次亜フッ素酸カルシウム(Ca(FO)2)、次亜フッ素酸バリウム(Ba(FO)2)等の次亜フッ素酸の塩;次亜塩素酸リチウム(LiClO)、次亜塩素酸ナトリウム(NaClO)、次亜塩素酸カリウム(KClO)、次亜塩素酸マグネシウム(Mg(ClO)2)、次亜塩素酸カルシウム(Ca(ClO)2)、次亜塩素酸バリウム(Ba(ClO)2)、次亜塩素酸t-ブチル(t-BuClO)、次亜塩素酸アンモニウム(NH4ClO)、次亜塩素酸トリエタノールアミン((CH2CH2OH)3N・ClO)等の次亜塩素酸の塩;次亜臭素酸リチウム(LiBrO)、次亜臭素酸ナトリウム(NaBrO)、次亜臭素酸カリウム(KBrO)、次亜臭素酸マグネシウム(Mg(BrO)2)、次亜臭素酸カルシウム(Ca(BrO)2)、次亜臭素酸バリウム(Ba(BrO)2)、次亜臭素酸アンモニウム(NH4BrO)、次亜臭素酸トリエタノールアミン((CH2CH2OH)3N・BrO)等の次亜臭素酸の塩;次亜ヨウ素酸リチウム(LiIO)、次亜ヨウ素酸ナトリウム(NaIO)、次亜ヨウ素酸カリウム(KIO)、次亜ヨウ素酸マグネシウム(Mg(IO)2)、次亜ヨウ素酸カルシウム(Ca(IO)2)、次亜ヨウ素酸バリウム(Ba(IO)2)、次亜ヨウ素酸アンモニウム(NH4IO)、次亜ヨウ素酸トリエタノールアミン((CH2CH2OH)3N・IO)等の次亜ヨウ素酸の塩等が挙げられる。これらハロゲン原子を含有する酸化剤は、単独でもまたは2種以上混合しても用いることができる。
本発明の研磨用組成物は、アミド結合を含有する有機化合物を含む。該有機化合物は、-CO-NR-(COの部分は二重結合)で表されるアミド結合を分子中に有する化合物である。かような有機化合物を含むことにより、本発明の研磨用組成物に含まれる酸化剤の分解を抑制し、かつIV族材料を含む層を保護する保護膜を形成する役割を果たすため、IV族材料の溶解を防止することができる。
本発明の研磨用組成物は、さらに砥粒を含むことが好ましい。砥粒は、研磨対象物を機械的に研磨する作用を有し、研磨用組成物による研磨対象物の研磨速度を向上させる。
本発明の研磨用組成物のpHは、5以上であることが好ましく、7以上であることがより好ましい。また、本発明の研磨用組成物のpHは、12以下であることが好ましく、10以下であることがより好ましい。この範囲であれば、研磨対象物の過剰な溶解を抑制しながら効率的な研磨を実施することができる。
本発明の研磨用組成物は、各成分を分散または溶解するための分散媒または溶媒として水を含むことが好ましい。他の成分の作用を阻害することを抑制するという観点から、不純物をできる限り含有しない水が好ましく、具体的には、イオン交換樹脂にて不純物イオンを除去した後、フィルタを通して異物を除去した純水や超純水、または蒸留水が好ましい。
本発明の研磨用組成物は、必要に応じて、金属防食剤、防腐剤、防カビ剤、水溶性高分子、難溶性の有機物を溶解するための有機溶媒等の他の成分をさらに含んでもよい。以下、好ましい他の成分である、金属防食剤、防腐剤、および防カビ剤について説明する。
研磨用組成物中に金属防食剤を加えることにより、研磨用組成物を用いた研磨で配線の脇に凹みが生じるのをより抑えることができる。また、研磨用組成物を用いて研磨した後の研磨対象物の表面にディッシングが生じるのをより抑えることができる。
本発明で用いられる防腐剤および防カビ剤としては、例えば、2-メチル-4-イソチアゾリン-3-オンや5-クロロ-2-メチル-4-イソチアゾリン-3-オン等のイソチアゾリン系防腐剤、パラオキシ安息香酸エステル類、およびフェノキシエタノール等が挙げられる。これら防腐剤および防カビ剤は、単独でもまたは2種以上混合して用いてもよい。
本発明の研磨用組成物の製造方法は、特に制限されず、例えば、ハロゲン原子を含有する酸化剤およびアミド結合を含有する有機化合物、および必要に応じて他の成分を、水中で攪拌混合することにより得ることができる。
上述のように、本発明の研磨用組成物は、特に、IV族材料を含む層を有する研磨対象物の研磨に好適に用いられる。よって、本発明は、IV族材料を含む層を有する研磨対象物を本発明の研磨用組成物で研磨する研磨方法を提供する。また、本発明は、IV族材料を含む層を有する研磨対象物を前記研磨方法で研磨する工程を含む基板の製造方法を提供する。
表1に示すアミド結合を含有する有機化合物を、表1に示す組成物中の含有量となるように添加した。また、酸化剤として次亜塩素酸ナトリウムの水溶液(濃度:5.9質量%)または過酸化水素水溶液(濃度:31質量%)を、組成物中の含有量として0.03質量%となるように水中で攪拌混合し(混合温度:約25℃、混合時間:約10分)、実施例1~9および比較例1~29の研磨用組成物を調製した。研磨用組成物のpHは、水酸化カリウム(KOH)を加え調整し、pHメータにより確認した。
Ge基板のエッチングレートは、浸漬条件:3cm×3cmのGe基板を、43℃で5分間浸漬させ(攪拌子を300rpmで回転させながら)、その後の重量変化から溶解量を算出し、その溶解量を浸漬時間で除して、Ge基板のエッチングレートを測定した。
砥粒として平均一次粒子径が30nm、平均二次粒子径が62nmであるコロイダルシリカ、ハロゲンを含有する酸化剤としてNaClO、アミド基を含有する有機化合物として下記表3に記載の化合物を、それぞれ下記表3に示すような含有量で、水中で攪拌混合し(混合温度:約25℃、混合時間:約10分)、実施例10~19および比較例30~46の研磨用組成物を調製した。研磨用組成物のpHは、硝酸(HNO3)または水酸化カリウム(KOH)を加え、pH8.5に調整した。
Ge基板およびTEOS基板について、実施例10~19および比較例30~46の研磨用組成物を用いて、下記表2に示す研磨条件で一定時間研磨したときの研磨速度を求めた。Ge基板〔結晶方位(100)〕を3cm×3cmにクーポン化して使用した。Ge基板の研磨速度は、研磨前後の重量の差分から求めた。また、TEOS基板の研磨速度は、光干渉式膜厚測定装置を用いて測定される研磨前後のそれぞれの膜の厚みの差を、研磨時間で除することで求めた。
Claims (5)
- ハロゲン原子を含有する酸化剤と、
アミド結合を含有する有機化合物と、
を含む、研磨用組成物。 - IV族材料を含む層を有する研磨対象物を研磨する用途で使用される、請求項1に記載の研磨用組成物。
- さらに砥粒を含む、請求項1または2に記載の研磨用組成物。
- IV族材料を含む層を有する研磨対象物を請求項1~3のいずれか1項に記載の研磨用組成物で研磨する、研磨方法。
- IV族材料を含む層を有する研磨対象物を請求項4に記載の研磨方法で研磨する工程を含む、基板の製造方法。
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EP3774647A4 (en) * | 2018-03-28 | 2022-04-06 | FUJIFILM Electronic Materials U.S.A, Inc. | CHEMICAL-MECHANICAL POLISHING COMPOSITION FOR RUTHENIUM MATERIALS |
WO2023127775A1 (ja) * | 2021-12-28 | 2023-07-06 | 株式会社レゾナック | 組成物、研磨剤および基材の研磨方法 |
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US10907073B2 (en) * | 2017-01-11 | 2021-02-02 | Fujimi Incorporated | Polishing composition |
EP3761345A4 (en) * | 2018-03-02 | 2021-04-28 | Mitsubishi Gas Chemical Company, Inc. | COMPOSITION WITH SUPPRESSED ALUMINUM DAMAGE AND PROCESS FOR MANUFACTURING A SEMICONDUCTOR SUBSTRATE THEREFORE |
WO2019190730A2 (en) * | 2018-03-28 | 2019-10-03 | Fujifilm Electronic Materials U.S.A., Inc. | Barrier ruthenium chemical mechanical polishing slurry |
US10815392B2 (en) * | 2018-05-03 | 2020-10-27 | Rohm and Haas Electronic CMP Holdings, Inc. | Chemical mechanical polishing method for tungsten |
JP7133414B2 (ja) * | 2018-09-20 | 2022-09-08 | 株式会社フジミインコーポレーテッド | 研磨用組成物 |
US11525071B2 (en) * | 2020-03-30 | 2022-12-13 | Fujimi Incorporated | Polishing composition based on mixture of colloidal silica particles |
JP7523291B2 (ja) | 2020-09-14 | 2024-07-26 | 株式会社フジミインコーポレーテッド | 研磨用組成物、研磨方法、および半導体基板の製造方法 |
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KR102022139B1 (ko) * | 2012-03-16 | 2019-09-17 | 가부시키가이샤 후지미인코퍼레이티드 | 연마용 조성물 |
US20150060400A1 (en) * | 2012-04-18 | 2015-03-05 | Fujimi Incorporated | Polishing composition |
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EP3774647A4 (en) * | 2018-03-28 | 2022-04-06 | FUJIFILM Electronic Materials U.S.A, Inc. | CHEMICAL-MECHANICAL POLISHING COMPOSITION FOR RUTHENIUM MATERIALS |
US11999876B2 (en) | 2018-03-28 | 2024-06-04 | Fujifilm Electronic Materials U.S.A., Inc. | Bulk ruthenium chemical mechanical polishing composition |
WO2023127775A1 (ja) * | 2021-12-28 | 2023-07-06 | 株式会社レゾナック | 組成物、研磨剤および基材の研磨方法 |
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