TW202323463A - Chemical mechanical polishing composition, and polishing method - Google Patents
Chemical mechanical polishing composition, and polishing method Download PDFInfo
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- TW202323463A TW202323463A TW111128869A TW111128869A TW202323463A TW 202323463 A TW202323463 A TW 202323463A TW 111128869 A TW111128869 A TW 111128869A TW 111128869 A TW111128869 A TW 111128869A TW 202323463 A TW202323463 A TW 202323463A
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- Prior art keywords
- chemical mechanical
- mechanical polishing
- group
- acid
- composition
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- 238000005498 polishing Methods 0.000 title claims abstract description 219
- 239000000126 substance Substances 0.000 title claims abstract description 179
- 239000000203 mixture Substances 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims description 22
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- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 89
- 239000011733 molybdenum Substances 0.000 claims abstract description 89
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 87
- 125000000524 functional group Chemical group 0.000 claims abstract description 73
- 150000003839 salts Chemical class 0.000 claims abstract description 50
- 239000006061 abrasive grain Substances 0.000 claims abstract description 36
- 239000004065 semiconductor Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 125000003277 amino group Chemical group 0.000 claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 239000011163 secondary particle Substances 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 23
- 150000001450 anions Chemical class 0.000 claims description 20
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 19
- 150000001768 cations Chemical class 0.000 claims description 14
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- 239000007789 gas Substances 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000004313 iron ammonium citrate Substances 0.000 description 1
- 235000000011 iron ammonium citrate Nutrition 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- AQBLLJNPHDIAPN-MUCWUPSWSA-K iron(3+);(e)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C/C(C)=O.C\C([O-])=C/C(C)=O.C\C([O-])=C/C(C)=O AQBLLJNPHDIAPN-MUCWUPSWSA-K 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- MIHDRTUWKXQGKN-UHFFFAOYSA-N n,n-dimethylmethanamine;hexadecane;hydrate Chemical compound O.CN(C)C.CCCCCCCCCCCCCCCC MIHDRTUWKXQGKN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWLXDPFBEPBAQB-UHFFFAOYSA-N orthoperiodic acid Chemical compound OI(O)(O)(O)(O)=O TWLXDPFBEPBAQB-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 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
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 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
- 239000000523 sample Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 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
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 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
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- STYCVOUVPXOARC-UHFFFAOYSA-M trimethyl(octyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCC[N+](C)(C)C STYCVOUVPXOARC-UHFFFAOYSA-M 0.000 description 1
- OLNCQUXQEJCISO-UHFFFAOYSA-M trimethyl(propyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](C)(C)C OLNCQUXQEJCISO-UHFFFAOYSA-M 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Description
本發明是有關於一種化學機械研磨用組成物及使用其的研磨方法。The invention relates to a composition for chemical mechanical polishing and a polishing method using the same.
伴隨著半導體積體電路的製造技術的提高,要求半導體元件的高積體化、高速運行。與此相伴,在半導體元件中的微細電路的製造步驟中所要求的半導體基板表面的平坦性變得更嚴格,化學機械研磨(Chemical Mechanical Polishing,CMP)成為半導體元件的製造步驟中不可缺少的技術。Along with the improvement of the manufacturing technology of semiconductor integrated circuits, high-integration and high-speed operation of semiconductor elements are required. Along with this, the flatness of the surface of the semiconductor substrate required in the manufacturing process of the fine circuit in the semiconductor device has become stricter, and chemical mechanical polishing (CMP) has become an indispensable technology in the manufacturing process of the semiconductor device .
CMP是如下的技術:將化學機械研磨用組成物供給至貼附於平台上的研磨用墊上,將半導體基板推壓至研磨用墊,使半導體基板與研磨用墊相互滑動,藉此對半導體基板化學性且機械性地進行研磨。在CMP中,可藉由利用試劑的化學反應及利用研磨粒的機械研磨,磨削半導體基板表面的凹凸而使其表面平坦化。CMP is a technique of supplying a composition for chemical mechanical polishing to a polishing pad attached to a table, pressing the semiconductor substrate against the polishing pad, and sliding the semiconductor substrate and the polishing pad against each other, thereby polishing the semiconductor substrate. Grinding is performed chemically and mechanically. In CMP, the roughness on the surface of the semiconductor substrate can be ground to planarize the surface by chemical reaction of reagents and mechanical polishing with abrasive grains.
近年來,為了改善製作經由此種CMP製造的半導體基板的銅配線時的銅向凹部的埋入性,研究了使用釕膜或鉬膜的方法(例如,參照專利文獻1~專利文獻3)。 [現有技術文獻] [專利文獻] In recent years, methods using a ruthenium film or a molybdenum film have been studied in order to improve the embedding property of copper in concave portions when forming copper wiring of a semiconductor substrate produced by such CMP (for example, refer to Patent Document 1 to Patent Document 3). [Prior art literature] [Patent Document]
[專利文獻1]日本專利特表2009-514219號公報 [專利文獻2]日本專利特表2010-535424號公報 [專利文獻3]國際公開第2019/151145號 [Patent Document 1] Japanese Patent Application Publication No. 2009-514219 [Patent Document 2] Japanese Patent Application Publication No. 2010-535424 [Patent Document 3] International Publication No. 2019/151145
[發明所欲解決之課題] 在此種CMP中,在研磨對象包含釕的情況下,為了抑制揮發性高的四氧化釕氣體的產生,對包含釕的部位進行研磨,需要使用鹼性的化學機械研磨用組成物、過碘酸鉀或次氯酸鉀般的具有高氧化力的鹵素系氧化劑進行化學機械研磨。但是,若使用鹼性的化學機械研磨用組成物,雖然可抑制四氧化釕氣體的產生,但氧化不充分的氧化釕會附著於研磨用墊表面,使研磨用墊的研磨特性劣化。其結果,難以一邊維持穩定的研磨速度一邊對包含釕的半導體基板進行化學機械研磨。另一方面,在研磨對象包含釕或鉬的情況下,需要使用具有高氧化力的氧化劑,但例如在使用具有高氧化力的鹵素系氧化劑的情況下,有可能使釕或鉬腐蝕。 [Problem to be Solved by the Invention] In such CMP, when the polishing object contains ruthenium, in order to suppress the generation of highly volatile ruthenium tetroxide gas and polish the part containing ruthenium, it is necessary to use an alkaline chemical mechanical polishing composition, iodine Chemical-mechanical polishing is carried out with a halogen-based oxidant with high oxidizing power such as potassium chloride or potassium hypochlorite. However, if an alkaline chemical mechanical polishing composition is used, the generation of ruthenium tetroxide gas can be suppressed, but insufficiently oxidized ruthenium oxide adheres to the surface of the polishing pad, deteriorating the polishing properties of the polishing pad. As a result, it is difficult to chemically mechanically polish a semiconductor substrate containing ruthenium while maintaining a stable polishing rate. On the other hand, when the polishing target contains ruthenium or molybdenum, it is necessary to use an oxidizing agent with high oxidizing power. However, if a halogen-based oxidizing agent with high oxidizing power is used, for example, ruthenium or molybdenum may be corroded.
本發明的幾個形態提供一種化學機械研磨用組成物,所述化學機械研磨用組成物可抑制釕或鉬的腐蝕,同時一邊維持穩定的研磨速度一邊對包含釕或鉬的半導體基板進行化學機械研磨。 [解決課題之手段] Several aspects of the present invention provide a composition for chemical mechanical polishing that suppresses corrosion of ruthenium or molybdenum and performs chemical mechanical polishing on a semiconductor substrate containing ruthenium or molybdenum while maintaining a stable polishing rate. grind. [Means to solve the problem]
本發明是為了解決所述課題的至少一部分而成者,可作為以下的任一形態來實現。The present invention is made to solve at least a part of the above-mentioned problems, and can be realized as any of the following aspects.
本發明的化學機械研磨用組成物的一形態含有: 研磨粒(A);以及 化合物(D),具有選自由胺基及其鹽所組成的群組中的至少一種官能基、以及選自由羧基及其鹽所組成的群組中的至少一種官能基, 所述研磨粒(A)具有下述通式(1)至下述通式(4)所表示的官能基中的至少一種官能基。 -SO 3 -M +・・・・・(1) -COO -M +・・・・・(2) (所述式(1)及所述式(2)中,M +表示一價陽離子) -NR 1R 2・・・・・(3) -N +R 1R 2R 3M -・・・・・(4) (所述式(3)及所述式(4)中,R 1、R 2及R 3分別獨立地表示氫原子、或經取代或者未經取代的烴基,M -表示陰離子) One aspect of the chemical mechanical polishing composition of the present invention includes: abrasive grains (A); and a compound (D) having at least one functional group selected from the group consisting of amine groups and salts thereof, and a functional group selected from carboxyl groups At least one functional group in the group consisting of the following general formula (1) to the following general formula (4), the abrasive grain (A) has at least one functional group. -SO 3 - M +・・・・・(1) -COO - M +・・・・・(2) (In the above formula (1) and the above formula (2), M + represents a monovalent cation) -NR 1 R 2・・・・・(3) -N + R 1 R 2 R 3 M -・・・・・(4) (In the above formula (3) and the above formula (4), R 1 , R 2 and R 3 independently represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group, M - represents an anion)
在所述化學機械研磨用組成物的一形態中, 所述化合物(D)的含量可為0.005質量%~5質量%。 In one form of the composition for chemical mechanical polishing, The content of the compound (D) may be 0.005% by mass to 5% by mass.
在所述化學機械研磨用組成物的任一形態中, 化學機械研磨用組成物中的所述研磨粒(A)的仄他電位的絕對值可為10 mV以上。 In any form of the composition for chemical mechanical polishing, The absolute value of the zeta potential of the abrasive grains (A) in the chemical mechanical polishing composition may be 10 mV or more.
在所述化學機械研磨用組成物的任一形態中, pH可為6以上且12以下。 In any form of the composition for chemical mechanical polishing, The pH may be 6 or more and 12 or less.
在所述化學機械研磨用組成物的任一形態中, pH可為1.5以上且4以下。 In any form of the composition for chemical mechanical polishing, The pH may be 1.5 or more and 4 or less.
在所述化學機械研磨用組成物的任一形態中, 化學機械研磨用組成物中的所述研磨粒(A)的平均二次粒徑可為5 nm以上且70 nm以下。 In any form of the composition for chemical mechanical polishing, The abrasive grains (A) in the chemical mechanical polishing composition may have an average secondary particle diameter of not less than 5 nm and not more than 70 nm.
本發明的研磨方法的一形態包括: 使用所述任一形態的化學機械研磨用組成物對半導體基板進行研磨的步驟。 A form of the grinding method of the present invention includes: A step of polishing a semiconductor substrate using any one of the chemical mechanical polishing compositions described above.
在所述研磨方法的一形態中, 所述半導體基板可包括由選自由釕、鉬、釕合金及鉬合金所組成的群組中的至少一種構成的部位。 [發明的效果] In one form of the grinding method, The semiconductor substrate may include a portion composed of at least one selected from the group consisting of ruthenium, molybdenum, a ruthenium alloy, and a molybdenum alloy. [Effect of the invention]
根據本發明的化學機械研磨用組成物,可抑制釕或鉬的腐蝕,同時一邊維持穩定的研磨速度一邊對包含釕或鉬的半導體基板進行化學機械研磨。According to the composition for chemical mechanical polishing of the present invention, it is possible to chemically mechanically polish a semiconductor substrate containing ruthenium or molybdenum while maintaining a stable polishing rate while suppressing corrosion of ruthenium or molybdenum.
以下,對本發明的較佳實施方式進行詳細說明。再者,本發明並不限定於下述實施方式,亦包括於不變更本發明的主旨的範圍內實施的各種變形例。Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modification examples implemented in the range which does not change the summary of this invention are included.
於本說明書中,如「A~B」般記載的數值範圍被解釋為包含數值A作為下限值,並且包含數值B作為上限值。In this specification, the numerical range described as "A-B" is interpreted as including numerical value A as a lower limit, and including numerical value B as an upper limit.
1.化學機械研磨用組成物 本發明的一實施方式的化學機械研磨用組成物含有:研磨粒(A)(本說明書中亦稱為「成分(A)」);以及化合物(D)(本說明書中亦稱為「成分(D)」),具有選自由胺基及其鹽所組成的群組中的至少一種官能基、以及選自由羧基及其鹽所組成的群組中的至少一種官能基,所述研磨粒(A)具有下述通式(1)至下述通式(4)所表示的官能基中的至少一種官能基。 -SO 3 -M +・・・・・(1) -COO -M +・・・・・(2) (所述式(1)及所述式(2)中,M +表示一價陽離子) -NR 1R 2・・・・・(3) -N +R 1R 2R 3M -・・・・・(4) (所述式(3)及所述式(4)中,R 1、R 2及R 3分別獨立地表示氫原子、或經取代或者未經取代的烴基;M -表示陰離子) 以下,對本實施方式的化學機械研磨用組成物中所含的各成分進行詳細說明。 1. Chemical Mechanical Polishing Composition A chemical mechanical polishing composition according to an embodiment of the present invention contains: abrasive grains (A) (also referred to as "component (A)" in this specification); and compound (D) (this Instructions are also referred to as "ingredient (D)"), having at least one functional group selected from the group consisting of amine groups and their salts, and at least one functional group selected from the group consisting of carboxyl groups and their salts The abrasive grain (A) has at least one functional group among the functional groups represented by the following general formula (1) to the following general formula (4). -SO 3 - M +・・・・・(1) -COO - M +・・・・・(2) (In the above formula (1) and the above formula (2), M + represents a monovalent cation) -NR 1 R 2・・・・・(3) -N + R 1 R 2 R 3 M -・・・・・(4) (In the above formula (3) and the above formula (4), R 1 , R 2 and R 3 each independently represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group; M − represents an anion) Hereinafter, each component contained in the chemical mechanical polishing composition of the present embodiment will be described in detail.
1.1. 成分(A) 本實施方式的化學機械研磨用組成物含有研磨粒(A)。作為成分(A),可列舉:二氧化矽、氧化鈰、氧化鋁、氧化鋯、二氧化鈦等無機粒子,其中較佳為二氧化矽粒子。作為二氧化矽粒子,可列舉煙熏二氧化矽、膠體二氧化矽等,其中較佳為膠體二氧化矽。就減少劃痕等研磨缺陷的觀點而言,較佳使用膠體二氧化矽。作為膠體二氧化矽,例如可使用藉由日本專利特開2003-109921號公報等中記載的方法製造的膠體二氧化矽。 1.1. Composition (A) The chemical mechanical polishing composition of the present embodiment contains abrasive grains (A). Examples of the component (A) include inorganic particles such as silica, ceria, alumina, zirconia, and titania, among which silica particles are preferred. Examples of silica particles include fumed silica and colloidal silica, among which colloidal silica is preferred. From the viewpoint of reducing polishing defects such as scratches, colloidal silica is preferably used. As colloidal silica, colloidal silica produced by the method described in Unexamined-Japanese-Patent No. 2003-109921 etc. can be used, for example.
在成分(A)為將二氧化矽作為主成分的二氧化矽粒子的情況下,成分(A)可更含有其他成分。作為其他成分,可列舉鋁化合物、矽化合物等。藉由二氧化矽粒子更含有鋁化合物或矽化合物,可減小二氧化矽粒子的表面硬度,因此存在可於維持穩定的研磨速度的同時,進一步減少被研磨面的研磨損傷或凹陷的產生的情況。When the component (A) is silica particles having silica as a main component, the component (A) may further contain other components. Examples of other components include aluminum compounds, silicon compounds, and the like. Since the silica particles further contain aluminum compounds or silicon compounds, the surface hardness of the silica particles can be reduced. Therefore, it is possible to further reduce the occurrence of grinding damage or dents on the polished surface while maintaining a stable grinding speed. Condition.
作為鋁化合物,例如可列舉:氫氧化鋁、氧化鋁(氧化鋁(alumina))、氯化鋁、氮化鋁、乙酸鋁、磷酸鋁、硫酸鋁、鋁酸鈉、鋁酸鉀等。另一方面,作為矽化合物,可列舉氮化矽、碳化矽、矽酸鹽、矽酮、矽樹脂等。Examples of the aluminum compound include aluminum hydroxide, aluminum oxide (alumina), aluminum chloride, aluminum nitride, aluminum acetate, aluminum phosphate, aluminum sulfate, sodium aluminate, potassium aluminate, and the like. On the other hand, examples of the silicon compound include silicon nitride, silicon carbide, silicate, silicone, and silicone resin.
成分(A)的形狀並無特別限定,可為球狀,亦可為繭狀,亦可為連鎖球狀,亦可在表面具有多個突起。在表面具有多個突起的研磨粒例如可應用日本專利特開2007-153732號公報或日本專利特開2013-121631號公報中所記載的方法來製造。The shape of the component (A) is not particularly limited, and may be spherical, cocoon-like, interlocking spherical, or may have a plurality of protrusions on the surface. Abrasive grains having a plurality of protrusions on the surface can be produced by applying, for example, the method described in JP-A-2007-153732 or JP-A-2013-121631.
成分(A)的仄他電位的絕對值在化學機械研磨用組成物中較佳為10 mV以上,更佳為15 mV以上,特佳為20 mV以上。若成分(A)的仄他電位的絕對值處於所述範圍,則藉由研磨粒間的靜電排斥力有效果地防止粒子彼此的凝聚,並且可以更穩定的研磨速度對包含釕或鉬的半導體基板進行研磨。再者,作為仄他電位測定裝置,可列舉:大塚電子公司製造的「ELSZ-2000ZS」、馬爾文(Malvern)公司製造的「傑塔思傑尤塔(Zetasizer Ultra)」、美國分散技術公司(Dispersion Technology Inc.)製造的「DT300」等。The absolute value of the zeta potential of the component (A) is preferably at least 10 mV, more preferably at least 15 mV, and most preferably at least 20 mV in the composition for chemical mechanical polishing. If the absolute value of the zeta potential of the component (A) is in the above range, the aggregation of the particles can be effectively prevented by the electrostatic repulsion force between the abrasive particles, and the semiconductor containing ruthenium or molybdenum can be treated at a more stable grinding speed. The substrate is ground. In addition, examples of the zeta potential measuring device include "ELSZ-2000ZS" manufactured by Otsuka Electronics Co., Ltd., "Zetasizer Ultra" manufactured by Malvern Corporation, and Dispersion Technology Inc. ( "DT300" manufactured by Dispersion Technology Inc., etc.
在研磨對象包含釕的情況下,化學機械研磨用組成物中的成分(A)的平均二次粒徑較佳為20 nm以上,更佳為50 nm以上。在研磨對象包含釕的情況下,化學機械研磨用組成物中的成分(A)的平均二次粒徑較佳為70 nm以下,更佳為60 nm以下。成分(A)的平均二次粒徑處於所述範圍時,可獲得對釕膜的充分的研磨速度,並且可獲得不產生粒子的沈降、分離而穩定性優異的化學機械研磨用組成物。再者,化學機械研磨用組成物中的成分(A)的平均二次粒徑可使用利用動態光散射法進行的粒度分佈測定裝置來測定。作為此種粒度分佈測定裝置,例如可列舉馬爾文(Malvern)公司製造的型號「傑塔思傑尤塔(Zetasizer Ultra)」。再者,平均二次粒徑藉由體積換算而算出。When the object to be polished contains ruthenium, the average secondary particle diameter of the component (A) in the chemical mechanical polishing composition is preferably 20 nm or more, more preferably 50 nm or more. When the object to be polished contains ruthenium, the average secondary particle diameter of the component (A) in the chemical mechanical polishing composition is preferably 70 nm or less, more preferably 60 nm or less. When the average secondary particle size of the component (A) is within the above range, a sufficient polishing rate for the ruthenium film can be obtained, and a composition for chemical mechanical polishing having excellent stability without particle settling or separation can be obtained. In addition, the average secondary particle size of the component (A) in the composition for chemical mechanical polishing can be measured using a particle size distribution measuring device performed by a dynamic light scattering method. As such a particle size distribution measuring device, for example, a model "Zetasizer Ultra" manufactured by Malvern Co., Ltd. is mentioned. In addition, the average secondary particle diameter was calculated by volume conversion.
在研磨對象包含鉬的情況下,化學機械研磨用組成物中的成分(A)的平均二次粒徑較佳為5 nm以上,更佳為7 nm以上。在研磨對象包含鉬的情況下,化學機械研磨用組成物中的成分(A)的平均二次粒徑較佳為70 nm以下,更佳為60 nm以下。成分(A)的平均二次粒徑處於所述範圍時,由於為小粒徑,因此機械研磨性能降低,但由於表面自由能增大,故與鉬的反應性提高,因此可獲得對鉬膜的充分的研磨速度,並且可獲得不產生粒子的沈降、分離而穩定性優異的化學機械研磨用組成物。When the object to be polished contains molybdenum, the average secondary particle diameter of the component (A) in the chemical mechanical polishing composition is preferably 5 nm or more, more preferably 7 nm or more. When the object to be polished contains molybdenum, the average secondary particle size of the component (A) in the chemical mechanical polishing composition is preferably 70 nm or less, more preferably 60 nm or less. When the average secondary particle size of the component (A) is within the above range, the mechanical polishing performance is reduced due to the small particle size, but the reactivity with molybdenum is improved due to the increase in surface free energy, so that a molybdenum film can be obtained. It is possible to obtain a chemical mechanical polishing composition having a sufficient polishing rate and excellent stability without causing particle settling or separation.
成分(A)的表面的至少一部分具有下述通式(1)至下述通式(4)所表示的官能基(以下亦稱為「特定官能基」)中的至少一種官能基。 -SO 3 -M +・・・・・(1) -COO -M +・・・・・(2) (所述式(1)及所述式(2)中,M +表示一價陽離子) -NR 1R 2・・・・・(3) -N +R 1R 2R 3M -・・・・・(4) (所述式(3)及所述式(4)中,R 1、R 2及R 3分別獨立地表示氫原子、或經取代或者未經取代的烴基;M -表示陰離子) At least a part of the surface of the component (A) has at least one functional group among the functional groups represented by the following general formula (1) to the following general formula (4) (hereinafter also referred to as "specific functional group"). -SO 3 - M +・・・・・(1) -COO - M +・・・・・(2) (In the above formula (1) and the above formula (2), M + represents a monovalent cation) -NR 1 R 2・・・・・(3) -N + R 1 R 2 R 3 M -・・・・・(4) (In the above formula (3) and the above formula (4), R 1 , R 2 and R 3 independently represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group; M - represents an anion)
表面的至少一部分被特定官能基修飾的研磨粒與未被特定官能基進行表面修飾的研磨粒相比,仄他電位的絕對值變大,因此研磨粒之間的靜電排斥力增大。其結果,化學機械研磨用組成物中的研磨粒的分散性提高,因此可在減少研磨損傷或凹陷的產生的同時進行高速研磨。Abrasive grains whose surface is at least partly modified with a specific functional group have a larger absolute value of zeta potential than abrasive grains whose surface is not modified with a specific functional group, thus increasing the electrostatic repulsion between abrasive grains. As a result, the dispersibility of the abrasive grains in the chemical mechanical polishing composition is improved, so high-speed polishing can be performed while reducing the occurrence of polishing damage and dishing.
成分(A)可具有下述通式(1)所表示的官能基。 -SO 3 -M +・・・・・(1) (M +表示一價陽離子) Component (A) may have a functional group represented by the following general formula (1). -SO 3 - M +・・・・・(1) (M + means monovalent cation)
所述通式(1)中,作為M +所表示的一價陽離子,並不限定於該些,例如可列舉H +、Li +、Na +、K +、NH 4 +。即、所述通式(1)所表示的官能基亦可改稱為「選自由磺基及其鹽所組成的群組中的至少一種官能基」。此處,所謂「磺基的鹽」,是指用Li +、Na +、K +、NH 4 +等一價陽離子取代磺基(-SO 3H)中所含的氫離子而得的官能基。具有所述通式(1)所表示的官能基的成分(A)是於其表面經由共價鍵固定有所述通式(1)所表示的官能基的研磨粒,且不包含於其表面物理性或離子性吸附有具有所述通式(1)所表示的官能基的化合物的研磨粒。 In the general formula (1), the monovalent cation represented by M + is not limited to these, and examples thereof include H + , Li + , Na + , K + , and NH 4 + . That is, the functional group represented by the general formula (1) may also be referred to as "at least one functional group selected from the group consisting of sulfo groups and salts thereof". Here, the "salt of the sulfo group" refers to a functional group obtained by substituting a monovalent cation such as Li + , Na + , K + , NH 4 + for the hydrogen ion contained in the sulfo group (-SO 3 H) . The component (A) having the functional group represented by the general formula (1) is an abrasive grain in which the functional group represented by the general formula (1) is immobilized on its surface through a covalent bond, and is not contained on the surface Abrasive grains in which a compound having a functional group represented by the general formula (1) is physically or ionically adsorbed.
具有所述通式(1)所表示的官能基的成分(A)可以如下方式進行製造。首先,藉由將由公知的方法製成的二氧化矽及含巰基的矽烷偶合劑於酸性介質中充分攪拌,可使含巰基的矽烷偶合劑共價鍵結於二氧化矽的表面。此處,作為含巰基的矽烷偶合劑,例如可列舉3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷等。接下來,進而適量添加過氧化氫並充分放置,藉此可獲得具有所述通式(1)所表示的官能基的成分(A)。The component (A) having a functional group represented by the general formula (1) can be produced as follows. First, the mercapto-containing silane coupling agent can be covalently bonded to the surface of the silica by fully stirring the silicon dioxide and the mercapto-containing silane coupling agent prepared by a known method in an acidic medium. Here, examples of the mercapto group-containing silane coupling agent include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. Next, by further adding an appropriate amount of hydrogen peroxide and leaving it to stand sufficiently, the component (A) having the functional group represented by the general formula (1) can be obtained.
具有所述通式(1)所表示的官能基的成分(A)的仄他電位於化學機械研磨用組成物中為負電位,其負電位較佳為-10 mV以下,更佳為-15 mV以下,特佳為-20 mV以下。若成分(A)的仄他電位處於所述範圍,則存在藉由研磨粒間的靜電排斥力有效果地防止粒子彼此的凝聚,並且可以更穩定的研磨速度對包含釕或鉬的半導體基板進行研磨的情況。再者,仄他電位測定裝置可使用所述的裝置。成分(A)的仄他電位可藉由適當增減所述含巰基的矽烷偶合劑等的添加量來調整。The zeta potential of the component (A) having the functional group represented by the general formula (1) is a negative potential in the composition for chemical mechanical polishing, and the negative potential is preferably -10 mV or less, more preferably -15 mV. Below mV, preferably below -20 mV. If the zeta potential of the component (A) is in the above-mentioned range, the aggregation of particles can be effectively prevented by the electrostatic repulsion force between the abrasive particles, and the semiconductor substrate containing ruthenium or molybdenum can be polished at a more stable polishing rate. Grinding condition. In addition, the above-mentioned device can be used for the zeta potential measuring device. The zeta potential of the component (A) can be adjusted by appropriately increasing or decreasing the added amount of the mercapto-containing silane coupling agent or the like.
於本實施方式的化學機械研磨用組成物含有具有所述通式(1)所表示的官能基的成分(A)的情況下,當將化學機械研磨用組成物的總質量設為100質量%時,成分(A)(質量%)的含量較佳為0.5質量%以上,更佳為1質量%以上。當將化學機械研磨用組成物的總質量設為100質量%時,成分(A)的含量(質量%)較佳為10質量%以下,更佳為5質量%以下。若具有所述通式(1)所表示的官能基的成分(A)的含量處於所述範圍,則存在可以穩定的研磨速度對包含釕或鉬的半導體基板進行研磨,並且化學機械研磨用組成物的保存穩定性變得良好的情況。In the case where the chemical mechanical polishing composition of the present embodiment contains the component (A) having a functional group represented by the general formula (1), when the total mass of the chemical mechanical polishing composition is taken as 100% by mass , the content of the component (A) (mass %) is preferably at least 0.5 mass %, more preferably at least 1 mass %. When the total mass of the chemical mechanical polishing composition is 100% by mass, the content (% by mass) of the component (A) is preferably at most 10% by mass, more preferably at most 5% by mass. If the content of the component (A) having the functional group represented by the general formula (1) is within the above-mentioned range, a semiconductor substrate containing ruthenium or molybdenum can be polished at a stable polishing rate, and the chemical mechanical polishing composition When the storage stability of the substance becomes good.
成分(A)可具有下述通式(2)所表示的官能基。 -COO -M +・・・・・(2) (M +表示一價陽離子) Component (A) may have a functional group represented by the following general formula (2). -COO - M +・・・・・(2) (M + means monovalent cation)
所述通式(2)中,作為M +所表示的一價陽離子,並不限定於該些,例如可列舉H +、Li +、Na +、K +、NH 4 +。即、所述通式(2)所表示的官能基亦可改稱為「選自由羧基及其鹽所組成的群組中的至少一種官能基」。此處,所謂「羧基的鹽」,是指用Li +、Na +、K +、NH 4 +等一價陽離子取代羧基(-COOH)中所含的氫離子而得的官能基。具有所述通式(2)所表示的官能基的成分(A)是於其表面經由共價鍵固定有所述通式(2)所表示的官能基的研磨粒,且不包含於其表面物理性或離子性吸附有具有所述通式(2)所表示的官能基的化合物的研磨粒。 In the general formula (2), the monovalent cation represented by M + is not limited to these, and examples thereof include H + , Li + , Na + , K + , and NH 4 + . That is, the functional group represented by the general formula (2) may also be referred to as "at least one functional group selected from the group consisting of carboxyl group and its salt". Here, the "salt of a carboxyl group" refers to a functional group in which a hydrogen ion contained in a carboxyl group (-COOH) is replaced with a monovalent cation such as Li + , Na + , K + , or NH 4 + . The component (A) having the functional group represented by the general formula (2) is an abrasive grain in which the functional group represented by the general formula (2) is immobilized on its surface through a covalent bond, and is not contained on the surface Abrasive grains in which a compound having a functional group represented by the general formula (2) is physically or ionically adsorbed.
具有所述通式(2)所表示的官能基的成分(A)可以如下方式進行製造。首先,將由公知的方法製成的二氧化矽及含羧酸酐的矽烷偶合劑於鹼性介質中充分攪拌,使含羧酸酐的矽烷偶合劑共價鍵結於研磨粒的表面,藉此可獲得具有所述通式(2)所表示的官能基的研磨粒。此處,作為含羧酸酐的矽烷偶合劑,例如可列舉3-(三乙氧基矽烷基)丙基琥珀酸酐等。The component (A) having a functional group represented by the general formula (2) can be produced as follows. First, fully stir the silicon dioxide and the silane coupling agent containing carboxylic anhydride in an alkaline medium, so that the silane coupling agent containing carboxylic anhydride is covalently bonded to the surface of the abrasive grains, thereby obtaining Abrasive grains having a functional group represented by the general formula (2). Here, as a silane coupling agent containing a carboxylic acid anhydride, 3-(triethoxysilyl) propyl succinic anhydride etc. are mentioned, for example.
具有所述通式(2)所表示的官能基的成分(A)的仄他電位於化學機械研磨用組成物中為負電位,其負電位較佳為-10 mV以下,更佳為-15 mV以下,特佳為-20 mV以下。若成分(A)的仄他電位處於所述範圍,則存在藉由研磨粒間的靜電排斥力有效果地防止粒子彼此的凝聚,並且可以更穩定的研磨速度對包含釕或鉬的半導體基板進行研磨的情況。再者,仄他電位測定裝置可使用所述的裝置。具有所述通式(2)所表示的官能基的成分(A)的仄他電位可藉由適當增減所述含羧酸酐的矽烷偶合劑等的添加量來調整。The zeta potential of the component (A) having the functional group represented by the general formula (2) is a negative potential in the composition for chemical mechanical polishing, and the negative potential is preferably -10 mV or less, more preferably -15 mV. Below mV, preferably below -20 mV. If the zeta potential of the component (A) is in the above-mentioned range, the aggregation of particles can be effectively prevented by the electrostatic repulsion force between the abrasive particles, and the semiconductor substrate containing ruthenium or molybdenum can be polished at a more stable polishing rate. Grinding condition. In addition, the above-mentioned device can be used for the zeta potential measuring device. The zeta potential of the component (A) having the functional group represented by the general formula (2) can be adjusted by appropriately increasing or decreasing the added amount of the carboxylic anhydride-containing silane coupling agent or the like.
於本實施方式的化學機械研磨用組成物含有所述通式(2)所表示的成分(A)的情況下,當將化學機械研磨用組成物的總質量設為100質量%時,成分(A)的含量較佳為0.1質量%以上,更佳為0.3質量%以上,特佳為0.5質量%以上。當將化學機械研磨用組成物的總質量設為100質量%時,成分(A)的含量較佳為10質量%以下,更佳為8質量%以下,特佳為5質量%以下。若成分(A)的含量處於所述範圍,則存在可以穩定的研磨速度對包含釕或鉬的半導體基板進行研磨,並且化學機械研磨用組成物的保存穩定性變得良好的情況。In the case where the chemical mechanical polishing composition of the present embodiment contains the component (A) represented by the general formula (2), when the total mass of the chemical mechanical polishing composition is taken as 100% by mass, the component ( The content of A) is preferably at least 0.1% by mass, more preferably at least 0.3% by mass, and most preferably at least 0.5% by mass. When the total mass of the chemical mechanical polishing composition is 100% by mass, the content of the component (A) is preferably at most 10% by mass, more preferably at most 8% by mass, and most preferably at most 5% by mass. When the content of the component (A) is in the above range, the semiconductor substrate containing ruthenium or molybdenum can be polished at a stable polishing rate, and the storage stability of the chemical mechanical polishing composition may become good.
成分(A)可具有下述通式(3)及/或下述通式(4)所表示的官能基。 -NR 1R 2・・・・・(3) -N +R 1R 2R 3M -・・・・・(4) (所述式(3)及所述式(4)中,R 1、R 2及R 3分別獨立地表示氫原子、或經取代或者未經取代的烴基;M -表示陰離子) The component (A) may have a functional group represented by the following general formula (3) and/or the following general formula (4). -NR 1 R 2・・・・・(3) -N + R 1 R 2 R 3 M -・・・・・(4) (In the above formula (3) and the above formula (4), R 1 , R 2 and R 3 independently represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group; M - represents an anion)
所述通式(3)所表示的官能基表示胺基,所述通式(4)所表示的官能基表示胺基的鹽。因此,亦可將所述通式(3)所表示的官能基及所述通式(4)所表示的官能基彙總而改稱為「選自由胺基及其鹽所組成的群組中的至少一種官能基」。具有所述通式(3)及/或所述通式(4)所表示的官能基的成分(A)是於其表面經由共價鍵固定有所述通式(3)及/或所述通式(4)所表示的官能基的研磨粒,且不包含於其表面物理性或離子性吸附有具有所述通式(3)及/或所述通式(4)所表示的官能基的化合物的研磨粒。The functional group represented by the general formula (3) represents an amine group, and the functional group represented by the general formula (4) represents a salt of an amine group. Therefore, the functional groups represented by the general formula (3) and the functional groups represented by the general formula (4) can also be collectively referred to as "selected from the group consisting of amine groups and their salts". at least one functional group". The component (A) having the functional group represented by the general formula (3) and/or the general formula (4) has the general formula (3) and/or the Abrasive grains with functional groups represented by the general formula (4), and do not contain the functional groups represented by the general formula (3) and/or the general formula (4) on their surface physically or ionically adsorbed Abrasive grains of compounds.
所述通式(4)中,作為M -所表示的陰離子,並不限定於該些,例如除了OH -、F -、Cl -、Br -、I -、CN -等陰離子以外,亦可列舉源於酸性化合物的陰離子。 In the general formula (4), the anion represented by M - is not limited to these, for example, in addition to anions such as OH - , F - , Cl - , Br - , I - , CN -, etc., there may also be mentioned Anions derived from acidic compounds.
所述通式(3)及所述通式(4)中,R 1~R 3分別獨立地表示氫原子、或經取代或者未經取代的烴基,但R 1~R 3中的兩個以上亦可鍵結而形成環結構。 In the general formula (3) and the general formula (4), R 1 to R 3 each independently represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group, but two or more of R 1 to R 3 It can also be bonded to form a ring structure.
作為R 1~R 3所表示的烴基,可為脂肪族烴基、芳香族烴基、芳香脂肪族烴基或脂環式烴基的任一者。另外,脂肪族烴基及芳香脂肪族烴基的脂肪族可為飽和亦可為不飽和,可為直鏈狀亦可為分支狀。作為該些烴基,例如可列舉直鏈狀、分支狀、或環狀的烷基、烯基、芳烷基及芳基等。 The hydrocarbon groups represented by R 1 to R 3 may be any of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an araliphatic hydrocarbon group, or an alicyclic hydrocarbon group. In addition, the aliphatic group of the aliphatic hydrocarbon group and the araliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched. Examples of these hydrocarbon groups include linear, branched, or cyclic alkyl groups, alkenyl groups, aralkyl groups, and aryl groups.
作為烷基,較佳為碳數為1~6的低級烷基,更佳為碳數為1~4的低級烷基。作為此種烷基,例如可列舉:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基、新戊基、正己基、異己基、第二己基、第三己基、環戊基、環己基等。The alkyl group is preferably a lower alkyl group having 1 to 6 carbon atoms, more preferably a lower alkyl group having 1 to 4 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-pentyl, isopentyl, Second pentyl, third pentyl, neopentyl, n-hexyl, isohexyl, second hexyl, third hexyl, cyclopentyl, cyclohexyl and the like.
作為烯基,較佳為碳數為1~6的低級烯基,更佳為碳數為1~4的低級烯基。作為此種烯基,例如可列舉乙烯基、正丙烯基、異丙烯基、正丁烯基、異丁烯基、第二丁烯基、第三丁烯基等。The alkenyl group is preferably a lower alkenyl group having 1 to 6 carbon atoms, more preferably a lower alkenyl group having 1 to 4 carbon atoms. As such an alkenyl group, a vinyl group, n-propenyl group, isopropenyl group, n-butenyl group, isobutenyl group, second butenyl group, third butenyl group etc. are mentioned, for example.
作為芳烷基,較佳為碳數為7~12者。作為此種芳烷基,例如可列舉苄基、苯乙基、苯基丙基、苯基丁基、苯基己基、甲基苄基、甲基苯乙基、乙基苄基等。As an aralkyl group, those with 7-12 carbon atoms are preferable. Examples of such aralkyl groups include benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylhexyl, methylbenzyl, methylphenethyl, ethylbenzyl and the like.
作為芳基,較佳為碳數為6~14者。作為此種芳基,例如可列舉苯基、鄰甲苯基、間甲苯基、對甲苯基、2,3-二甲苯基、2,4-二甲苯基、2,5-二甲苯基、2,6-二甲苯基、3,5-二甲苯基、萘基、蒽基等。As an aryl group, those with 6-14 carbon atoms are preferable. Examples of such aryl groups include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2, 6-xylyl, 3,5-xylyl, naphthyl, anthracenyl, etc.
所述芳基及芳烷基的芳香環亦可具有例如甲基、乙基等低級烷基或鹵素原子、硝基、胺基、羥基等作為取代基。The aromatic ring of the aryl group and aralkyl group may have, for example, a lower alkyl group such as a methyl group or an ethyl group, a halogen atom, a nitro group, an amino group, a hydroxyl group, or the like as a substituent.
具有所述通式(3)及/或所述通式(4)所表示的官能基的成分(A)例如藉由將二氧化矽與含胺基的矽烷偶合劑在酸性介質中充分攪拌,使含胺基的矽烷偶合劑共價鍵結於二氧化矽的表面,可製造具有所述通式(3)及/或所述通式(4)所表示的官能基的研磨粒。此處,作為含胺基的矽烷偶合劑,例如可列舉:3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷等。The component (A) having the functional group represented by the general formula (3) and/or the general formula (4) is, for example, fully stirred with the silane coupling agent containing an amino group in an acidic medium, Abrasive grains having the functional groups represented by the general formula (3) and/or the general formula (4) can be produced by covalently bonding the amino group-containing silane coupling agent to the surface of the silica. Here, examples of the amino group-containing silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and the like.
在化學機械研磨用組成物的pH為6以上且12以下的情況下,具有所述通式(3)及/或所述通式(4)所表示的官能基的成分(A)的仄他電位於化學機械研磨用組成物中為負電位,其負電位較佳為-10 mV以下,更佳為-15 mV以下。在化學機械研磨用組成物的pH為1.5以上且4以下的情況下,具有所述通式(3)及/或所述通式(4)所表示的官能基的成分(A)的仄他電位為正電位,其正電位較佳為10 mV以上,更佳為15 mV以上。若成分(A)的仄他電位處於所述範圍,則存在藉由研磨粒間的靜電排斥力有效果地防止粒子彼此的凝聚,並且可以更穩定的研磨速度對包含釕或鉬的半導體基板進行研磨的情況。再者,仄他電位測定裝置可使用所述的裝置。具有所述通式(3)及/或所述通式(4)所表示的官能基的成分(A)的仄他電位可藉由適當增減所述含胺基的矽烷偶合劑等的添加量來調整。When the pH of the composition for chemical mechanical polishing is 6 to 12, the pH of the component (A) having the functional group represented by the general formula (3) and/or the general formula (4) is other Electricity is a negative potential in the chemical mechanical polishing composition, and the negative potential is preferably -10 mV or less, more preferably -15 mV or less. When the pH of the composition for chemical mechanical polishing is 1.5 to 4, the pH of the component (A) having the functional group represented by the general formula (3) and/or the general formula (4) is other The potential is a positive potential, and the positive potential is preferably at least 10 mV, more preferably at least 15 mV. If the zeta potential of the component (A) is in the above-mentioned range, the aggregation of particles can be effectively prevented by the electrostatic repulsion force between the abrasive particles, and the semiconductor substrate containing ruthenium or molybdenum can be polished at a more stable polishing rate. Grinding condition. In addition, the above-mentioned device can be used for the zeta potential measuring device. The zeta potential of the component (A) having the functional group represented by the general formula (3) and/or the general formula (4) can be adjusted by appropriately increasing or decreasing the addition of the amine-containing silane coupling agent, etc. amount to adjust.
於本實施方式的化學機械研磨用組成物含有具有所述通式(3)及/或所述通式(4)所表示的官能基的成分(A)的情況下,當將化學機械研磨用組成物的總質量設為100質量%時,成分(A)的含量較佳為0.1質量%以上,更佳為0.5質量%以上,特佳為1質量%以上。當將化學機械研磨用組成物的總質量設為100質量%時,成分(A)的含量較佳為10質量%以下,更佳為8質量%以下,特佳為5質量%以下。若成分(A)的含量處於所述範圍,則存在可以穩定的研磨速度對包含釕或鉬的半導體基板進行研磨,並且化學機械研磨用組成物的保存穩定性變得良好的情況。In the case where the composition for chemical mechanical polishing of this embodiment contains the component (A) having the functional group represented by the general formula (3) and/or the general formula (4), when the composition for chemical mechanical polishing When the total mass of the composition is 100% by mass, the content of the component (A) is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and most preferably at least 1% by mass. When the total mass of the chemical mechanical polishing composition is 100% by mass, the content of the component (A) is preferably at most 10% by mass, more preferably at most 8% by mass, and most preferably at most 5% by mass. When the content of the component (A) is in the above range, the semiconductor substrate containing ruthenium or molybdenum can be polished at a stable polishing rate, and the storage stability of the chemical mechanical polishing composition may become good.
1.2. 成分(D) 本實施方式的化學機械研磨用組成物含有具有選自由胺基及其鹽所組成的群組中的至少一種官能基、及選自由羧基及其鹽所組成的群組中的至少一種官能基的化合物(D)。成分(D)藉由吸附在含有釕或鉬的半導體基板的表面而形成保護膜,可抑制釕部位或鉬部位的過度腐蝕。 1.2. Composition (D) The chemical mechanical polishing composition of this embodiment contains at least one functional group selected from the group consisting of amine groups and their salts, and at least one functional group selected from the group consisting of carboxyl groups and their salts. compound (D). Component (D) forms a protective film by being adsorbed on the surface of a semiconductor substrate containing ruthenium or molybdenum, and suppresses excessive corrosion of ruthenium or molybdenum sites.
作為胺基及其鹽,可列舉下述通式(5)或下述通式(6)所表示的官能基。 -NR 4R 5・・・・・(5) -N +R 4R 5R 6M -・・・・・(6) (所述式(5)及所述式(6)中,R 4、R 5、及R 6各自獨立地表示氫原子、或經取代或者未經取代的烴基;M -表示陰離子) Examples of the amine group and its salt include functional groups represented by the following general formula (5) or the following general formula (6). -NR 4 R 5・・・・・(5) -N + R 4 R 5 R 6 M -・・・・・(6) (In the above formula (5) and the above formula (6), R 4 , R 5 , and R 6 each independently represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group; M - represents an anion)
所述通式(5)及所述通式(6)中,R 4~R 6各自獨立地表示氫原子、或經取代或者未經取代的烴基,R 4~R 6中的兩個以上可鍵結而形成環結構。 In the general formula (5) and the general formula (6), R 4 to R 6 each independently represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group, and two or more of R 4 to R 6 may be bonds to form a ring structure.
作為R 4~R 6所表示的烴基,可為脂肪族烴基、芳香族烴基、芳香脂肪族烴基或脂環式烴基的任一者。另外,脂肪族烴基及芳香脂肪族烴基的脂肪族可為飽和亦可為不飽和,可為直鏈狀亦可為分支狀。作為該些烴基,例如可列舉直鏈狀、分支狀、或環狀的烷基、烯基、芳烷基及芳基等。 The hydrocarbon group represented by R 4 to R 6 may be any of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an araliphatic hydrocarbon group, or an alicyclic hydrocarbon group. In addition, the aliphatic group of the aliphatic hydrocarbon group and the araliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or branched. Examples of these hydrocarbon groups include linear, branched, or cyclic alkyl groups, alkenyl groups, aralkyl groups, and aryl groups.
作為烷基,較佳為碳數為1~6的低級烷基,更佳為碳數為1~4的低級烷基。作為此種烷基,例如可列舉:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、異戊基、第二戊基、第三戊基、新戊基、正己基、異己基、第二己基、第三己基、環戊基、環己基等。The alkyl group is preferably a lower alkyl group having 1 to 6 carbon atoms, more preferably a lower alkyl group having 1 to 4 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-pentyl, isopentyl, Second pentyl, third pentyl, neopentyl, n-hexyl, isohexyl, second hexyl, third hexyl, cyclopentyl, cyclohexyl and the like.
作為烯基,較佳為碳數為1~6的低級烯基,更佳為碳數為1~4的低級烯基。作為此種烯基,例如可列舉:乙烯基、正丙烯基、異丙烯基、正丁烯基、異丁烯基、第二丁烯基、第三丁烯基等。The alkenyl group is preferably a lower alkenyl group having 1 to 6 carbon atoms, more preferably a lower alkenyl group having 1 to 4 carbon atoms. As such an alkenyl group, a vinyl group, a n-propenyl group, an isopropenyl group, a n-butenyl group, an isobutenyl group, a 2-butenyl group, a 3-butenyl group etc. are mentioned, for example.
作為芳烷基,較佳為碳數為7~12者。作為此種芳烷基,例如可列舉:苄基、苯乙基、苯基丙基、苯基丁基、苯基己基、甲基苄基、甲基苯乙基、乙基苄基等。As an aralkyl group, those with 7-12 carbon atoms are preferable. As such an aralkyl group, a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylhexyl group, a methylbenzyl group, a methylphenethyl group, an ethylbenzyl group etc. are mentioned, for example.
作為芳基,較佳為碳數為6~14者。作為此種芳基,例如可列舉:苯基、鄰甲苯基、間甲苯基、對甲苯基、2,3-二甲苯基、2,4-二甲苯基、2,5-二甲苯基、2,6-二甲苯基、3,5-二甲苯基、萘基、蒽基等。As an aryl group, those with 6-14 carbon atoms are preferable. Examples of such aryl groups include: phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2 , 6-xylyl, 3,5-xylyl, naphthyl, anthracenyl, etc.
所述芳基及所述芳烷基的芳香環可具有例如甲基、乙基等低級烷基或鹵素原子、硝基、胺基、羥基等作為取代基。The aromatic ring of the aryl group and the aralkyl group may have, for example, a lower alkyl group such as a methyl group or an ethyl group, a halogen atom, a nitro group, an amino group, a hydroxyl group, or the like as a substituent.
作為羧基及其鹽,可列舉下述通式(7)所表示的官能基。 -COO -M +・・・・・(7) (M +表示一價陽離子) As a carboxyl group and its salt, the functional group represented by following General formula (7) is mentioned. -COO - M +・・・・・(7) (M + means monovalent cation)
所述通式(7)中,作為M +所表示的一價陽離子,並不限定於該些,例如可列舉H +、Li +、Na +、K +、NH 4 +。 In the general formula (7), the monovalent cation represented by M + is not limited to these, and examples thereof include H + , Li + , Na + , K + , and NH 4 + .
成分(D)只要是具有選自由胺基及其鹽所組成的群組中的至少一種官能基、及選自由羧基及其鹽所組成的群組中的至少一種官能基的結構,則並無特別限定,較佳為具有下述通式(8)所表示的結構。 -N(CH 2COO -M +) n(R 7) 2-n・・・・・(8) (所述式(8)中,R 7表示氫原子或經取代或者未經取代的烴基;M +表示一價陽離子;n表示1~2的整數) As long as component (D) has a structure having at least one functional group selected from the group consisting of amine groups and their salts, and at least one functional group selected from the group consisting of carboxyl groups and their salts, there is no It is particularly limited, and preferably has a structure represented by the following general formula (8). -N(CH 2 COO - M + ) n (R 7 ) 2-n・・・・・(8) (In the above formula (8), R 7 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group; M + represents a monovalent cation; n represents an integer of 1 to 2)
所述通式(8)中,作為R 7所表示的烴基,可列舉與所述通式(6)及所述通式(7)的R 4~R 6中例示的烴基相同的烴基。所述通式(8)中,作為M +所表示的一價陽離子,並不限定於該些,例如可列舉:H +、Li +、Na +、K +、NH 4 +。 In the general formula (8), examples of the hydrocarbon group represented by R 7 include the same hydrocarbon groups as those exemplified for R 4 to R 6 in the general formula (6) and the general formula (7). In the general formula (8), the monovalent cation represented by M + is not limited to these, and examples thereof include H + , Li + , Na + , K + , and NH 4 + .
藉由使成分(D)具有所述通式(8)所表示的結構,成分(D)有效果地配位並吸附於釕或鉬的表面而形成保護膜,藉此可抑制釕部位或鉬部位的過度腐蝕。By allowing the component (D) to have the structure represented by the general formula (8), the component (D) is effectively coordinated and adsorbed on the surface of ruthenium or molybdenum to form a protective film, thereby suppressing the ruthenium site or molybdenum Excessive corrosion of parts.
作為成分(D),例如可列舉:N-(膦醯基甲基)亞胺基二乙酸、羥乙基亞胺基二乙酸、氮基三乙酸、N-(2-羧乙基)亞胺基二乙酸、乙二胺四乙酸、L-麩胺酸二乙酸四鈉、甘胺酸-N,N-雙(亞甲基膦酸)、3,3',3''-氮基三丙酸、二醇醚二胺四乙酸、羥乙基乙二胺三乙酸、1,3-丙二胺-N,N,N',N'-四乙酸、三伸乙基四胺六乙酸、二羥乙基甘胺酸、(S,S)-乙二胺二琥珀酸三水合物、亞胺基二乙酸、反-1,2-二胺基環己烷-N,N,N',N'-四乙酸水合物等。該些成分(D)可單獨使用一種,亦可將兩種以上組合使用。Component (D) includes, for example, N-(phosphonomethyl)iminodiacetic acid, hydroxyethyliminodiacetic acid, nitrilotriacetic acid, N-(2-carboxyethyl)imine Diacetic acid, ethylenediaminetetraacetic acid, tetrasodium L-glutamine diacetate, glycine-N,N-bis(methylenephosphonic acid), 3,3',3''-nitrotripropyl acid, glycol ether diaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, 1,3-propanediamine-N,N,N',N'-tetraacetic acid, triethylenetetraaminehexaacetic acid, Hydroxyethylglycine, (S,S)-ethylenediaminedisuccinic acid trihydrate, iminodiacetic acid, trans-1,2-diaminocyclohexane-N,N,N',N '-tetraacetic acid hydrate, etc. These components (D) may be used alone or in combination of two or more.
當將化學機械研磨用組成物的總質量設為100質量%時,成分(D)的含量(質量%)較佳為0.05質量%以上,更佳為0.1質量%以上,特佳為0.15質量%以上。當將化學機械研磨用組成物的總質量設為100質量%時,成分(D)的含量(質量%)較佳為5質量%以下,更佳為2質量%以下,特佳為1質量%以下。若成分(D)的含量處於所述範圍,則存在可有效果地抑制含有釕或鉬的半導體基板的過度腐蝕。When the total mass of the chemical mechanical polishing composition is 100% by mass, the content (% by mass) of the component (D) is preferably at least 0.05% by mass, more preferably at least 0.1% by mass, and most preferably at least 0.15% by mass. above. When the total mass of the chemical mechanical polishing composition is 100% by mass, the content (% by mass) of the component (D) is preferably at most 5% by mass, more preferably at most 2% by mass, most preferably at most 1% by mass the following. When the content of the component (D) is within the above range, excessive corrosion of the semiconductor substrate containing ruthenium or molybdenum can be effectively suppressed.
1.3. 成分(B) 本實施方式的化學機械研磨用組成物可含有包含選自由過碘酸根離子(IO 4 -)、次氯酸根離子(ClO -)、亞氯酸根離子(ClO 2 -)及次溴酸根離子(BrO -)所組成的群組中的至少一種陰離子(以下,亦稱為「特定陰離子種」)的酸或其鹽(B)。推測成分(B)中所含的陰離子作為氧化劑發揮功能,使釕或鉬氧化而促進研磨。 1.3. Component (B) The chemical mechanical polishing composition of this embodiment may contain a composition selected from periodate ions (IO 4 - ), hypochlorite ions (ClO - ), chlorite ions (ClO 2 - ), and An acid or a salt (B) of at least one anion (hereinafter also referred to as “specific anion species”) in the group consisting of hypobromite ions (BrO − ). It is presumed that the anion contained in the component (B) functions as an oxidizing agent to oxidize ruthenium or molybdenum to promote polishing.
作為成分(B)的具體例,可列舉:過碘酸、亞氯酸、次氯酸、次溴酸、過碘酸鈉、過碘酸鉀、過碘酸銨、亞氯酸鈉、亞氯酸鉀、次氯酸鈉、次氯酸鉀、次溴酸鈉等。其中,較佳為選自由過碘酸、亞氯酸鉀、次氯酸鉀及次溴酸鈉所組成的群組中的至少一種化合物,更佳為過碘酸。成分(B)可單獨使用一種,亦可組合兩種以上使用。Specific examples of component (B) include periodic acid, chlorous acid, hypochlorous acid, hypobromous acid, sodium periodate, potassium periodate, ammonium periodate, sodium chlorite, and potassium chlorite , sodium hypochlorite, potassium hypochlorite, sodium hypobromite, etc. Among them, at least one compound selected from the group consisting of periodic acid, potassium chlorite, potassium hypochlorite and sodium hypobromite is preferred, and periodic acid is more preferred. Component (B) may be used alone or in combination of two or more.
相對於化學機械研磨用組成物1 L,成分(B)的含量(mol/L)較佳為0.001 mol/L以上,更佳為0.002 mol/L以上,特佳為0.003 mol/L以上。相對於化學機械研磨用組成物1L,成分(B)的含量(mol/L)較佳為0.05 mol/L以下,更佳為0.04 mol/L以下,特佳為0.035 mol/L以下。若成分(B)的含量處於所述範圍,則存在可使釕或鉬氧化而促進研磨,並且防止釕或鉬與特定陰離子種的過度反應,抑制釕或鉬的腐蝕的情況。The content (mol/L) of the component (B) is preferably at least 0.001 mol/L, more preferably at least 0.002 mol/L, and most preferably at least 0.003 mol/L with respect to 1 L of the chemical mechanical polishing composition. The content (mol/L) of the component (B) is preferably at most 0.05 mol/L, more preferably at most 0.04 mol/L, particularly preferably at most 0.035 mol/L, relative to 1 L of the chemical mechanical polishing composition. When the content of the component (B) is within the above range, ruthenium or molybdenum can be oxidized to promote grinding, and excessive reaction of ruthenium or molybdenum with a specific anion species can be prevented to suppress corrosion of ruthenium or molybdenum.
當將化學機械研磨用組成物的總質量設為100質量%時,成分(B)的含量(質量%)較佳為0.01質量%以上,更佳為0.05質量%以上,特佳為0.1質量%以上。當將化學機械研磨用組成物的總質量設為100質量%時,成分(B)的含量(質量%)較佳為10質量%以下,更佳為8質量%以下,特佳為7質量%以下。若成分(B)的含量處於所述範圍,則存在可使釕或鉬氧化而促進研磨,並且防止釕或鉬與特定陰離子種的過度反應,抑制釕或鉬的腐蝕的情況。When the total mass of the chemical mechanical polishing composition is 100% by mass, the content (% by mass) of the component (B) is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and most preferably at least 0.1% by mass above. When the total mass of the chemical mechanical polishing composition is 100% by mass, the content (% by mass) of the component (B) is preferably at most 10% by mass, more preferably at most 8% by mass, most preferably at most 7% by mass the following. When the content of the component (B) is within the above range, ruthenium or molybdenum can be oxidized to promote grinding, and excessive reaction of ruthenium or molybdenum with a specific anion species can be prevented to suppress corrosion of ruthenium or molybdenum.
1.4. 成分(C) 本實施方式的化學機械研磨用組成物可含有過氧化氫(C)(本說明書中亦稱為「成分(C)」)。過氧化氫(C)具有如下功能:使釕或鉬氧化而促進研磨,並且藉由成分(C)與釕或鉬反應而防止釕或鉬與成分(B)中所含的特定陰離子種的過度反應,而抑制鹵素氣體的產生或釕或鉬的腐蝕。 1.4. Composition (C) The chemical mechanical polishing composition of the present embodiment may contain hydrogen peroxide (C) (also referred to as "component (C)" in this specification). Hydrogen peroxide (C) has the following functions: it oxidizes ruthenium or molybdenum to promote grinding, and prevents ruthenium or molybdenum from reacting with ruthenium or molybdenum and the specific anion species contained in component (B). reaction, and suppress the generation of halogen gas or the corrosion of ruthenium or molybdenum.
相對於化學機械研磨用組成物1 L,成分(C)的含量(mol/L)較佳為0.0005 mol/L以上,更佳為0.0009 mol/L以上,特佳為0.0012 mol/L以上。相對於化學機械研磨用組成物1 L,成分(C)的含量(mol/L)較佳為0.5 mol/L以下,更佳為0.4 mol/L以下,特佳為0.3 mol/L以下。若成分(C)的含量處於所述範圍,則存在使釕或鉬氧化而促進研磨,並且藉由成分(C)與釕或鉬反應可防止釕或鉬與成分(B)中所含的特定陰離子種的過度反應,可抑制釕或鉬的腐蝕的情況。The content (mol/L) of the component (C) is preferably at least 0.0005 mol/L, more preferably at least 0.0009 mol/L, and most preferably at least 0.0012 mol/L with respect to 1 L of the chemical mechanical polishing composition. The content (mol/L) of the component (C) is preferably at most 0.5 mol/L, more preferably at most 0.4 mol/L, particularly preferably at most 0.3 mol/L, based on 1 L of the chemical mechanical polishing composition. If the content of the component (C) is in the above range, there will be oxidized ruthenium or molybdenum to promote grinding, and the reaction between the component (C) and the ruthenium or molybdenum can prevent the ruthenium or molybdenum from reacting with the specific compound contained in the component (B). Excessive reaction of anionic species can suppress the corrosion of ruthenium or molybdenum.
當將化學機械研磨用組成物的總質量設為100質量%時,成分(C)的含量(質量%)較佳為0.0017質量%以上,更佳為0.003質量%以上,特佳為0.004質量%以上。當將化學機械研磨用組成物的總質量設為100質量%時,成分(C)的含量(質量%)較佳為1.7質量%以下,更佳為1.4質量%以下,特佳為1質量%以下。若成分(C)的含量處於所述範圍,則存在使釕或鉬氧化而促進研磨,並且藉由成分(C)與釕或鉬反應可防止釕或鉬與成分(B)中所含的特定陰離子種的過度反應,可抑制釕或鉬的腐蝕的情況。When the total mass of the chemical mechanical polishing composition is 100% by mass, the content (% by mass) of the component (C) is preferably at least 0.0017% by mass, more preferably at least 0.003% by mass, most preferably at least 0.004% by mass above. When the total mass of the chemical mechanical polishing composition is 100% by mass, the content (% by mass) of the component (C) is preferably at most 1.7% by mass, more preferably at most 1.4% by mass, most preferably at most 1% by mass the following. If the content of the component (C) is in the above range, there will be oxidized ruthenium or molybdenum to promote grinding, and the reaction between the component (C) and the ruthenium or molybdenum can prevent the ruthenium or molybdenum from reacting with the specific compound contained in the component (B). Excessive reaction of anionic species can suppress the corrosion of ruthenium or molybdenum.
1.5.其他成分 本實施方式的化學機械研磨用組成物除了所述各成分以外,根據需要亦可含有液狀介質、鎓鹽、鐵(III)化合物、水溶性高分子、含氮雜環化合物、界面活性劑、有機酸及其鹽、無機酸及其鹽、鹼性化合物等。 1.5. Other ingredients The chemical mechanical polishing composition according to this embodiment may contain a liquid medium, an onium salt, an iron (III) compound, a water-soluble polymer, a nitrogen-containing heterocyclic compound, a surfactant, Organic acids and their salts, inorganic acids and their salts, basic compounds, etc.
<液狀介質> 本實施方式的化學機械研磨用組成物含有液狀介質。作為液狀介質,可列舉水、水與醇的混合介質、包含水及具有與水的相溶性的有機溶媒的混合介質等。該些中,較佳為使用水、水與醇的混合介質,更佳為使用水。作為水的原料,可較佳地使用純水。液狀介質作為所述各成分的剩餘部分調配即可。 <Liquid medium> The chemical mechanical polishing composition of this embodiment contains a liquid medium. Examples of the liquid medium include water, a mixed medium of water and alcohol, a mixed medium containing water and an organic solvent compatible with water, and the like. Among these, it is preferable to use water and a mixed medium of water and alcohol, and it is more preferable to use water. As a raw material of water, pure water can be preferably used. A liquid medium may be prepared as the remainder of each of the above-mentioned components.
<鎓鹽> 本實施方式的化學機械研磨用組成物可含有鎓鹽。認為鎓鹽吸附於鉬膜的表面而形成保護膜,降低鉬膜的腐蝕。作為鎓鹽,只要是包含鎓離子的化合物,則並無特別限定,較佳為下述通式(9)所表示的鎓鹽。 [化1] (式(9)中,R 8、R 9及R 10分別獨立地表示碳數為n個以下的烷基,R 11表示烷基、芳基或羥基;M -表示一價陰離子;n表示1以上的整數) <Onium Salt> The chemical mechanical polishing composition of the present embodiment may contain an onium salt. It is considered that the onium salt is adsorbed on the surface of the molybdenum film to form a protective film and reduce the corrosion of the molybdenum film. The onium salt is not particularly limited as long as it is a compound containing onium ions, but is preferably an onium salt represented by the following general formula (9). [chemical 1] (In formula (9), R 8 , R 9 and R 10 independently represent an alkyl group with n or less carbons, R 11 represents an alkyl group, an aryl group or a hydroxyl group; M - represents a monovalent anion; n represents 1 above integer)
作為所述通式(9)所表示的鎓鹽的具體例,可列舉:乙基三甲基氫氧化銨、丙基三甲基氫氧化銨、辛基三甲基氫氧化銨、十六烷基三甲基氫氧化銨、1-羥基乙基三甲基氫氧化銨、2-羥基乙基三甲基氫氧化銨、1-羥基丙基三甲基氫氧化銨、2-羥基丙基三甲基氫氧化銨、苄基三甲基氫氧化銨等。其中,較佳為乙基三甲基氫氧化銨、2-羥基乙基三甲基氫氧化銨。該些鎓鹽可單獨使用一種,亦可組合兩種以上來使用。Specific examples of the onium salt represented by the general formula (9) include: ethyltrimethylammonium hydroxide, propyltrimethylammonium hydroxide, octyltrimethylammonium hydroxide, hexadecane Trimethylammonium Hydroxide, 1-Hydroxyethyltrimethylammonium Hydroxide, 2-Hydroxyethyltrimethylammonium Hydroxide, 1-Hydroxypropyltrimethylammonium Hydroxide, 2-Hydroxypropyltrimethylammonium Hydroxide Methylammonium hydroxide, benzyltrimethylammonium hydroxide, etc. Among them, ethyltrimethylammonium hydroxide and 2-hydroxyethyltrimethylammonium hydroxide are preferred. These onium salts may be used alone or in combination of two or more.
在本實施方式的化學機械研磨用組成物含有鎓鹽的情況下,當將化學機械研磨用組成物的總質量設為100質量%時,鎓鹽的含量較佳為0.005質量%以上,更佳為0.01質量%以上。當將化學機械研磨用組成物的總質量設為100質量%時,鎓鹽的含量較佳為0.5質量%以下,更佳為0.4質量%以下。When the composition for chemical mechanical polishing according to this embodiment contains an onium salt, when the total mass of the composition for chemical mechanical polishing is 100% by mass, the content of the onium salt is preferably 0.005% by mass or more, more preferably 0.01% by mass or more. When the total mass of the chemical mechanical polishing composition is 100% by mass, the content of the onium salt is preferably at most 0.5% by mass, more preferably at most 0.4% by mass.
<鐵(III)化合物> 本實施方式的化學機械研磨用組成物可含有鐵(III)化合物。鐵(III)化合物有時可將鉬氧化而在鉬膜的表面形成脆弱的改質層,而促進鉬膜的研磨。 <Iron(III) compound> The chemical mechanical polishing composition of this embodiment may contain an iron (III) compound. Iron (III) compounds can sometimes oxidize molybdenum to form a fragile modified layer on the surface of the molybdenum film, thereby promoting the grinding of the molybdenum film.
鐵(III)化合物只要具有所述效果,則可為有機酸鐵鹽或無機酸鐵鹽的任一種。作為鐵(III)化合物,例如可列舉:硝酸鐵(III)、硫酸鐵銨(III)、高氯酸鐵(III)、氯化鐵(III)、硫酸鐵(III)、檸檬酸鐵(III)、檸檬酸鐵銨(III)、及草酸鐵銨(III)、乙醯丙酮鐵(III)等。這些鐵(III)化合物中,較佳為硝酸鐵(III)、檸檬酸鐵(III)、及乙醯丙酮鐵(III),特佳為硝酸鐵(III)。藉由使用該些鐵(III)化合物,可在鉬表面形成氧化物,可獲得容易利用成分(A)除去該氧化物,在抑制殘渣、凹陷及腐蝕的同時,良好地保持研磨速度並且具有平坦性的被研磨面。該些鐵(III)化合物可單獨使用一種,亦可組合兩種以上來使用。The iron (III) compound may be either an organic acid iron salt or an inorganic acid iron salt as long as it has the above effects. Examples of iron (III) compounds include: iron (III) nitrate, iron ammonium (III) sulfate, iron (III) perchlorate, iron (III) chloride, iron (III) sulfate, iron (III) citrate ), ferric ammonium citrate (III), ferric ammonium oxalate (III), iron acetylacetonate (III), etc. Among these iron (III) compounds, iron (III) nitrate, iron (III) citrate, and iron (III) acetylacetonate are preferred, and iron (III) nitrate is particularly preferred. By using these iron (III) compounds, oxides can be formed on the surface of molybdenum, and the oxides can be easily removed by component (A), while suppressing residue, pitting, and corrosion, while maintaining a good grinding speed and having a flat surface. Sexual ground surface. These iron (III) compounds may be used alone or in combination of two or more.
在本實施方式的化學機械研磨用組成物含有鐵(III)化合物的情況下,當將化學機械研磨用組成物的總質量設為100質量%時,鐵(III)化合物的含量較佳為0.001質量%以上,更佳為0.01質量%以上。當將化學機械研磨用組成物的總質量設為100質量%時,鐵(III)化合物的含量(質量%)較佳為1質量%以下,更佳為0.1質量%以下。認為鐵(III)化合物的含量處於所述範圍時,可有效果地使鉬的表面氧化,因此可進一步增大鉬的研磨速度,並且可有效果地抑制凹陷或腐蝕。When the composition for chemical mechanical polishing of this embodiment contains an iron (III) compound, when the total mass of the composition for chemical mechanical polishing is 100% by mass, the content of the iron (III) compound is preferably 0.001 mass % or more, more preferably 0.01 mass % or more. When the total mass of the chemical mechanical polishing composition is 100% by mass, the content (% by mass) of the iron (III) compound is preferably at most 1% by mass, more preferably at most 0.1% by mass. It is considered that when the content of the iron (III) compound is in the above range, the surface of molybdenum can be effectively oxidized, so the polishing rate of molybdenum can be further increased, and pitting and corrosion can be effectively suppressed.
<水溶性高分子> 本實施方式的化學機械研磨用組成物亦可含有水溶性高分子。水溶性高分子有時吸附於被研磨面的表面而降低研磨摩擦,從而可降低被研磨面的凹陷的產生。 <Water-soluble polymer> The chemical mechanical polishing composition of this embodiment may also contain a water-soluble polymer. Water-soluble polymers may be adsorbed on the surface of the surface to be polished to reduce polishing friction, thereby reducing the occurrence of dents on the surface to be polished.
作為水溶性高分子的具體例,可列舉多羧酸、聚苯乙烯磺酸、聚丙烯酸、聚甲基丙烯酸、聚醚、聚丙烯醯胺、聚乙烯醇、聚乙烯吡咯啶酮、聚乙烯亞胺、聚烯丙基胺、羥乙基纖維素等。該些可單獨使用一種或組合兩種以上使用。Specific examples of water-soluble polymers include polycarboxylic acid, polystyrenesulfonic acid, polyacrylic acid, polymethacrylic acid, polyether, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene Amine, polyallylamine, hydroxyethyl cellulose, etc. These can be used individually by 1 type or in combination of 2 or more types.
水溶性高分子的重量平均分子量(Mw)較佳為1萬以上且150萬以下,更佳為4萬以上且120萬以下。此處,「重量平均分子量」是指藉由凝膠滲透層析法(Gel Permeation Chromatography,GPC)測定的聚乙二醇換算的重量平均分子量。The weight average molecular weight (Mw) of the water-soluble polymer is preferably from 10,000 to 1.5 million, more preferably from 40,000 to 1.2 million. Here, the "weight average molecular weight" refers to the weight average molecular weight in terms of polyethylene glycol measured by gel permeation chromatography (Gel Permeation Chromatography, GPC).
於本實施方式的化學機械研磨用組成物含有水溶性高分子的情況下,於將化學機械研磨用組成物的總質量設為100質量%時,水溶性高分子的含量較佳為0.001質量%以上,更佳為0.002質量%以上。於將化學機械研磨用組成物的總質量設為100質量%時,水溶性高分子的含量較佳為0.1質量%以下,更佳為0.01質量%以下。In the case where the chemical mechanical polishing composition of the present embodiment contains a water-soluble polymer, when the total mass of the chemical mechanical polishing composition is taken as 100 mass%, the content of the water-soluble polymer is preferably 0.001 mass % or more, more preferably 0.002% by mass or more. When the total mass of the chemical mechanical polishing composition is 100% by mass, the content of the water-soluble polymer is preferably at most 0.1% by mass, more preferably at most 0.01% by mass.
<含氮雜環化合物> 含氮雜環化合物是指至少具有一個氮原子且包含選自雜五員環及雜六員環中的至少一種雜環的有機化合物。作為所述雜環的具體例,可列舉吡咯結構、咪唑結構、三唑結構等雜五員環;吡啶結構、嘧啶結構、噠嗪結構、吡嗪結構等雜六員環。所述雜環亦可形成縮合環。具體而言,可列舉:吲哚結構、異吲哚結構、苯並咪唑結構、苯並三唑結構、喹啉結構、異喹啉結構、喹唑啉結構、噌啉(cinnoline)結構、酞嗪結構、喹噁啉結構、吖啶結構等。於具有此種結構的雜環化合物中,較佳為具有吡啶結構、喹啉結構、苯並咪唑結構、苯並三唑結構的雜環化合物。 <Nitrogen-containing heterocyclic compounds> The nitrogen-containing heterocyclic compound refers to an organic compound having at least one nitrogen atom and containing at least one heterocyclic ring selected from heterocyclic five-membered rings and heterocyclic six-membered rings. Specific examples of the heterocyclic ring include hetero five-membered rings such as pyrrole structure, imidazole structure and triazole structure; and hetero six-membered rings such as pyridine structure, pyrimidine structure, pyridazine structure and pyrazine structure. The heterocyclic rings may also form condensed rings. Specifically, indole structure, isoindole structure, benzimidazole structure, benzotriazole structure, quinoline structure, isoquinoline structure, quinazoline structure, cinnoline (cinnoline) structure, phthalazine structure, quinoxaline structure, acridine structure, etc. Among heterocyclic compounds having such structures, heterocyclic compounds having pyridine structures, quinoline structures, benzimidazole structures, and benzotriazole structures are preferred.
作為含氮雜環化合物的具體例,可列舉氮丙啶、吡啶、嘧啶、吡咯啶、哌啶、吡嗪、三嗪、吡咯、咪唑、吲哚、喹啉、異喹啉、苯並異喹啉、嘌呤、喋啶(pteridine)、三唑、三唑啶、苯並三唑、羧基苯並三唑、及具有該些骨架的衍生物。該些中,較佳為選自由苯並三唑及三唑所組成的群組中的至少一種。該些含氮雜環化合物可單獨使用一種,亦可組合兩種以上使用。Specific examples of nitrogen-containing heterocyclic compounds include aziridine, pyridine, pyrimidine, pyrrolidine, piperidine, pyrazine, triazine, pyrrole, imidazole, indole, quinoline, isoquinoline, and benzisoquinone. Phine, purine, pteridine, triazole, triazolidine, benzotriazole, carboxybenzotriazole, and derivatives having these skeletons. Among these, at least one selected from the group consisting of benzotriazole and triazole is preferable. These nitrogen-containing heterocyclic compounds may be used alone or in combination of two or more.
<界面活性劑> 作為界面活性劑,並無特別限制,可使用陰離子性界面活性劑、陽離子性界面活性劑、非離子性界面活性劑等。作為陰離子性界面活性劑,例如可列舉:烷基醚硫酸鹽、聚氧乙烯烷基苯基醚硫酸鹽等硫酸鹽;全氟烷基化合物等含氟系界面活性劑等。作為陽離子性界面活性劑,例如可列舉脂肪族胺鹽、脂肪族銨鹽等。作為非離子性界面活性劑,例如可列舉乙炔二醇、乙炔二醇環氧乙烷加成物、乙炔醇等具有三鍵的非離子性界面活性劑;聚乙二醇型界面活性劑等。該些界面活性劑可單獨使用一種,亦可組合兩種以上使用。 <Surfactant> The surfactant is not particularly limited, and anionic surfactants, cationic surfactants, nonionic surfactants, and the like can be used. Examples of the anionic surfactant include: sulfates such as alkyl ether sulfates and polyoxyethylene alkylphenyl ether sulfates; fluorine-containing surfactants such as perfluoroalkyl compounds; and the like. As a cationic surfactant, an aliphatic amine salt, an aliphatic ammonium salt, etc. are mentioned, for example. Examples of the nonionic surfactant include nonionic surfactants having triple bonds such as acetylene glycol, acetylene glycol ethylene oxide adducts, and acetylene alcohol; polyethylene glycol-type surfactants; and the like. These surfactants may be used alone or in combination of two or more.
<有機酸及其鹽> 本實施方式的化學機械研磨用組成物可含有選自由有機酸及其鹽(除去所述成分(D))所組成的群組中的至少一種。有機酸及其鹽藉由與成分(A)的協同效應,有時可提高含有釕或鉬的半導體基板的研磨速度。 <Organic acids and their salts> The chemical mechanical polishing composition of this embodiment may contain at least one selected from the group consisting of organic acids and salts thereof (excluding the component (D)). An organic acid or a salt thereof may increase the polishing rate of a semiconductor substrate containing ruthenium or molybdenum due to a synergistic effect with the component (A).
作為有機酸及其鹽,較佳為具有羧基的化合物、具有磺基的化合物。作為具有羧基的化合物,例如可列舉:硬脂酸、月桂酸、油酸、肉豆蔻酸、烯基琥珀酸、乳酸、酒石酸、富馬酸、乙醇酸、鄰苯二甲酸、馬來酸、甲酸、乙酸、草酸、檸檬酸、蘋果酸、丙二酸、戊二酸、琥珀酸、苯甲酸、喹啉酸、喹哪啶酸、醯胺硫酸、丙酸、三氟乙酸;甘胺酸、丙胺酸、天冬胺酸、麩胺酸、離胺酸、精胺酸、色胺酸、十二烷基胺基乙基胺基乙基甘胺酸、芳香族胺基酸、雜環型胺基酸等胺基酸;烷基亞胺基二羧酸等亞胺基酸;及該些的鹽。作為具有磺基的化合物,例如可列舉十二烷基苯磺酸、對甲苯磺酸等烷基苯磺酸;丁基萘磺酸等烷基萘磺酸;十四烯磺酸等α-烯烴磺酸;及該些的鹽。該些化合物可單獨使用一種,亦可組合兩種以上使用。As organic acids and salts thereof, compounds having a carboxyl group and compounds having a sulfo group are preferable. Examples of compounds having a carboxyl group include stearic acid, lauric acid, oleic acid, myristic acid, alkenylsuccinic acid, lactic acid, tartaric acid, fumaric acid, glycolic acid, phthalic acid, maleic acid, formic acid , acetic acid, oxalic acid, citric acid, malic acid, malonic acid, glutaric acid, succinic acid, benzoic acid, quinolinic acid, quinaldinic acid, amidosulfuric acid, propionic acid, trifluoroacetic acid; glycine, propylamine Acid, aspartic acid, glutamic acid, lysine, arginine, tryptophan, dodecylaminoethylaminoethylglycine, aromatic amino acid, heterocyclic amino amino acid such as acid; imino acid such as alkyliminodicarboxylic acid; and their salts. Examples of compounds having a sulfo group include alkylbenzenesulfonic acids such as dodecylbenzenesulfonic acid and p-toluenesulfonic acid; alkylnaphthalenesulfonic acids such as butylnaphthalenesulfonic acid; and α-olefins such as tetradecenesulfonic acid. Sulfonic acids; and their salts. These compounds may be used alone or in combination of two or more.
於本實施方式的化學機械研磨用組成物含有有機酸(鹽)的情況下,於將化學機械研磨用組成物的總質量設為100質量%時,有機酸(鹽)的含量較佳為0.001質量%以上,更佳為0.01質量%以上。於將化學機械研磨用組成物的總質量設為100質量%時,有機酸(鹽)的含量較佳為5質量%以下,更佳為1質量%以下。When the composition for chemical mechanical polishing of this embodiment contains an organic acid (salt), when the total mass of the composition for chemical mechanical polishing is 100% by mass, the content of the organic acid (salt) is preferably 0.001 mass % or more, more preferably 0.01 mass % or more. When the total mass of the chemical mechanical polishing composition is 100% by mass, the content of the organic acid (salt) is preferably at most 5% by mass, more preferably at most 1% by mass.
<無機酸及其鹽> 作為無機酸,較佳為選自由鹽酸、硝酸、硫酸、磷酸、及該些的鹽所組成的群組中的至少一種。再者,無機酸亦可與化學機械研磨用組成物中另行添加的鹼形成鹽。 <Inorganic acids and their salts> The inorganic acid is preferably at least one selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and salts thereof. Furthermore, the inorganic acid may form a salt with a base additionally added to the chemical mechanical polishing composition.
<鹼性化合物> 作為鹼性化合物,可列舉有機鹼及無機鹼。作為有機鹼,較佳為胺,例如可列舉三乙胺、單乙醇胺、四甲基氫氧化銨、四乙基氫氧化銨、四丁基氫氧化銨、苄基胺、甲基胺、乙二胺、二甘醇胺、異丙胺等。作為無機鹼,例如可列舉氨、氫氧化鉀、氫氧化鈉等。該些鹼性化合物中,較佳為氨、氫氧化鉀。該些鹼性化合物可單獨使用一種,亦可組合兩種以上使用。 <Basic compounds> Examples of the basic compound include organic bases and inorganic bases. The organic base is preferably an amine, for example, triethylamine, monoethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzylamine, methylamine, ethylenediamine Amine, diglycolamine, isopropylamine, etc. As an inorganic base, ammonia, potassium hydroxide, sodium hydroxide etc. are mentioned, for example. Among these basic compounds, ammonia and potassium hydroxide are preferred. These basic compounds may be used alone or in combination of two or more.
1.6. pH 在研磨對象包含釕的情況下,本實施方式的化學機械研磨用組成物的pH較佳為6.0以上,更佳為6.5以上,特佳為7.0以上。在研磨對象包含釕的情況下,本實施方式的化學機械研磨用組成物的pH較佳為12.0以下,更佳為11.0以下,特佳為10.0以下。若pH處於所述範圍,則有時可有效果地抑制四氧化釕氣體的產生或釕的腐蝕。 1.6.pH When the object to be polished contains ruthenium, the pH of the chemical mechanical polishing composition of the present embodiment is preferably 6.0 or higher, more preferably 6.5 or higher, and particularly preferably 7.0 or higher. When the object to be polished contains ruthenium, the pH of the chemical mechanical polishing composition of the present embodiment is preferably 12.0 or less, more preferably 11.0 or less, particularly preferably 10.0 or less. When the pH is within the above range, the generation of ruthenium tetroxide gas or the corrosion of ruthenium may be effectively suppressed.
在研磨對象包含鉬的情況下,本實施方式的化學機械研磨用組成物的pH較佳為1.5以上,更佳為2.0以上。在研磨對象包含鉬的情況下,本實施方式的化學機械研磨用組成物的pH較佳為4.0以下,更佳為3.5以下。若pH處於所述範圍時,則有時可有效果地抑制鉬的腐蝕。When the object to be polished contains molybdenum, the pH of the chemical mechanical polishing composition of the present embodiment is preferably 1.5 or higher, more preferably 2.0 or higher. When the object to be polished contains molybdenum, the pH of the chemical mechanical polishing composition according to the present embodiment is preferably 4.0 or less, more preferably 3.5 or less. When the pH is within the above range, the corrosion of molybdenum may be effectively suppressed.
再者,化學機械研磨用組成物的pH例如可藉由添加所述的有機酸(鹽)、無機酸(鹽)、鹼性化合物等來調整,可使用該些中的一種以上。Furthermore, the pH of the composition for chemical mechanical polishing can be adjusted by adding the above-mentioned organic acid (salt), inorganic acid (salt), basic compound, etc., and one or more of them can be used.
本發明中,pH是指氫離子指數,其值可使用市售的pH計(例如,堀場製作所公司製造,桌上型pH計)進行測定。In the present invention, pH refers to a hydrogen ion index, and its value can be measured using a commercially available pH meter (eg, table-top pH meter manufactured by Horiba, Ltd.).
1.7. 化學機械研磨用組成物的製備方法 本實施方式的化學機械研磨用組成物可藉由使所述各成分溶解或分散於水等液狀介質中來製備。溶解或分散的方法並無特別限制,只要可均勻地溶解或分散,則可應用任何方法。另外,對所述各成分的混合順序、混合方法亦無特別限制。 1.7. Preparation method of composition for chemical mechanical polishing The chemical mechanical polishing composition of the present embodiment can be prepared by dissolving or dispersing the above components in a liquid medium such as water. The method of dissolution or dispersion is not particularly limited, and any method can be applied as long as it can be dissolved or dispersed uniformly. In addition, there is no particular limitation on the mixing order and mixing method of the above-mentioned components.
另外,化學機械研磨用組成物亦可作為濃縮類型的原液而製備,並於使用時利用水等液狀介質加以稀釋來使用。In addition, the composition for chemical mechanical polishing can also be prepared as a concentrated stock solution and diluted with a liquid medium such as water before use.
2. 研磨方法 本發明的一實施方式的研磨方法包括使用所述的化學機械研磨用組成物對半導體基板進行研磨的步驟。所述化學機械研磨用組成物可抑制釕或鉬的腐蝕,同時一邊維持穩定的研磨速度一邊對包含釕或鉬的半導體基板進行化學機械研磨。因此,作為被處理體的半導體基板較佳為包括由選自由釕、鉬、釕合金及鉬合金所組成的群組中的至少一種構成的部位。以下,參照圖1~圖4,對本實施方式的研磨方法進行詳細說明。 2. Grinding method A polishing method according to one embodiment of the present invention includes the step of polishing a semiconductor substrate using the composition for chemical mechanical polishing. The composition for chemical mechanical polishing suppresses corrosion of ruthenium or molybdenum, and performs chemical mechanical polishing on a semiconductor substrate containing ruthenium or molybdenum while maintaining a stable polishing rate. Therefore, it is preferable that the semiconductor substrate to be processed includes a portion composed of at least one selected from the group consisting of ruthenium, molybdenum, a ruthenium alloy, and a molybdenum alloy. Hereinafter, the polishing method of this embodiment will be described in detail with reference to FIGS. 1 to 4 .
作為包括由選自由釕、鉬、釕合金及鉬合金所組成的群組中的至少一種構成的部位的半導體基板,例如可列舉如圖1所示般的被處理體100。圖1中示出示意性地表示被處理體100的剖面圖。被處理體100經過以下的步驟(1)至步驟(4)來製作。As a semiconductor substrate including a portion composed of at least one selected from the group consisting of ruthenium, molybdenum, a ruthenium alloy, and a molybdenum alloy, for example, an object to be processed 100 as shown in FIG. 1 is exemplified. FIG. 1 shows a schematic cross-sectional view of an
(1)首先,如圖1所示,準備基體10。基體10例如可包括矽基板及形成於其上的氧化矽膜。進而,亦可於基體10上形成(未圖示)電晶體等功能器件。其次,使用熱氧化法於基體10之上形成作為絕緣膜的氧化矽膜12。(1) First, as shown in FIG. 1 , the
(2)繼而,對氧化矽膜12進行圖案化。將所獲得的圖案作為遮罩,藉由光微影術於氧化矽膜12形成配線用槽14。(2) Next, the
(3)繼而,於氧化矽膜12的表面及配線用槽14的內壁面形成含釕的膜16。含釕的膜16例如可藉由使用釕前驅物的化學氣相成長法(Chemical Vapour Deposition,CVD)或原子層堆積法(Atomic Layer Deposition,ALD)、或者濺鍍等物理氣相堆積法(Physical Vapor Deposition,PVD)來形成。再者,在所述步驟中,亦可形成含鉬的膜來代替含釕的膜16。含鉬的膜例如可藉由使用鉬前驅物的化學氣相成長法(CVD)或原子層堆積法(ALD)、或濺鍍等物理氣相堆積法(PVD)來形成。(3) Next, the ruthenium-containing
(4)繼而,藉由化學蒸鍍法或電鍍法,堆積膜厚10,000 Å~15,000 Å(此處,「Å」是指0.1 nm)的銅膜18。作為銅膜18的材料,不僅可使用純度高的銅,亦可使用含有銅的合金。作為含有銅的合金中的銅含量,較佳為95質量%以上。(4) Next, a
繼而,進行被處理體100的第一研磨步驟。圖2是示意性地表示第一研磨步驟結束時的被處理體100的剖面圖。如圖2所示,在第一研磨步驟中,使用銅膜用的化學機械研磨用組成物對銅膜18進行研磨直至露出含釕的膜16(或者含鉬的膜)。作為銅膜用的化學機械研磨用組成物,例如可列舉日本專利特開2010-153790號公報中記載的化學機械研磨用水系分散體。Next, the first grinding step of the object to be processed 100 is performed. FIG. 2 is a cross-sectional view schematically showing the
繼而,進行被處理體100的第二研磨步驟。圖3是示意性地表示第二研磨步驟結束時的被處理體100的剖面圖。如圖3所示,在第二研磨步驟中,使用本發明的化學機械研磨用組成物對含釕的膜16(或者含鉬的膜)、銅膜18、及氧化矽膜12的一部分進行研磨。Next, the second grinding step of the object to be processed 100 is performed. FIG. 3 is a cross-sectional view schematically showing the
於第一研磨步驟及第二研磨步驟中,例如可使用圖4所示般的研磨裝置200。圖4是示意性地表示研磨裝置200的立體圖。第一研磨步驟及第二研磨步驟是藉由自漿料供給噴嘴42供給漿料(化學機械研磨用組成物)44,且一邊使貼附有研磨用墊46的轉盤48旋轉,一邊將保持著半導體基板50的載架頭(carrier head)52抵接來進行。再者,圖4亦一併示出了水供給噴嘴54及修整器(dresser)56。In the first grinding step and the second grinding step, for example, a grinding
研磨用墊46的材質可為發泡聚胺基甲酸酯型、不織布型、麂皮型中的任一種,較佳為發泡聚胺基甲酸酯型。The material of the
載架頭52的研磨負荷可於0.7 psi~70 psi的範圍內選擇,較佳為1.5 psi~35 psi。另外,轉盤48及載架頭52的轉速可於10 rpm~400 rpm的範圍內適當選擇,較佳為30 rpm~150 rpm。自漿料供給噴嘴42供給的化學機械研磨用組成物的流量的下限值為15 mL/分,較佳為50 mL/分,其流量的上限值為400 mL/分,較佳為300 mL/分。The grinding load of the
作為市售的研磨裝置,例如可列舉:荏原製作所製造的型號「EPO-112」、「F-REX300SII」;藍邁斯特(Lapmaster)SFT製造的型號「LGP-510」、「LGP-552」;應用材料(Applied Material)製造的型號「米拉(Mirra)」、「瑞福興(Reflexion)」;G&P科技(TECHNOLOGY)製造的型號「POLI-400L」;AMAT製造的型號「瑞福興(Reflexion)LK」等。Examples of commercially available polishing devices include models "EPO-112" and "F-REX300SII" manufactured by Ebara Seisakusho, and models "LGP-510" and "LGP-552" manufactured by Lapmaster SFT. ; models "Mirra" and "Reflexion" manufactured by Applied Material; models "POLI-400L" manufactured by G&P Technology (TECHNOLOGY); models "Reflexion" manufactured by AMAT Reflexion) LK", etc.
3. 實施例 以下,藉由實施例對本發明進行說明,但本發明並不受該些實施例的任何限定。再者,本實施例中的「份」及「%」只要無特別說明則為質量基準。 3. Examples Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited by these examples. In addition, "part" and "%" in this Example are mass basis unless otherwise indicated.
3.1. 二氧化矽粒子水分散體的製備 3.1.1. 水分散體A的製備 在PL-3(扶桑化學工業公司製造,19.5%膠體二氧化矽分散液)2000 g中添加25%氨水(富士膠片和光純藥公司製造),調整為pH9。然後,滴加含(3-三乙氧基矽烷基)巰基的矽烷偶合劑(商品名「KBM-803」、信越化學工業公司製造)3.9 g,在60℃下攪拌2小時。然後,添加過氧化氫(富士膠片和光純藥公司製造)50 g,在常壓下回流8小時,獲得包含體積換算下的平均二次粒徑58 nm的利用磺基進行了表面修飾的繭型的二氧化矽粒子的水分散體A。再者,水分散體A~水分散體I中的各二氧化矽粒子的體積換算下的平均二次粒徑藉由粒度分佈測定裝置(馬爾文(Malvern)公司製造、型號「傑塔思傑尤塔(Zetasizer Ultra)」)來測定。 3.1. Preparation of aqueous dispersion of silica particles 3.1.1. Preparation of aqueous dispersion A 25% ammonia water (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 2000 g of PL-3 (manufactured by Fuso Chemical Industry Co., Ltd., 19.5% colloidal silica dispersion) to adjust the pH to 9. Then, 3.9 g of a (3-triethoxysilyl)mercapto group-containing silane coupling agent (trade name "KBM-803", manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise, and stirred at 60° C. for 2 hours. Then, 50 g of hydrogen peroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the mixture was refluxed at normal pressure for 8 hours to obtain a cocoon surface-modified with a sulfo group containing an average secondary particle diameter of 58 nm in terms of volume. Aqueous dispersion A of silica particles. Furthermore, the average secondary particle diameter of each silica particle in the aqueous dispersion A to aqueous dispersion I was calculated by the particle size distribution measuring device (manufactured by Malvern (Malvern), model "Jetta Sijie"). Uta (Zetasizer Ultra)") to measure.
3.1.2. 水分散體B的製備 將PL-3(扶桑化學工業公司製造,19.5%膠體二氧化矽分散液)2000 g加熱至60℃。然後,加入(3-三乙氧基矽烷基)丙基琥珀酸酐(東京化成工業公司製造)15.5 g,進而在60℃下攪拌4小時,獲得包含體積換算下的平均二次粒徑60 nm的利用羧基進行了表面修飾的繭型的二氧化矽粒子的水分散體B。 3.1.2. Preparation of aqueous dispersion B 2000 g of PL-3 (manufactured by Fuso Chemical Industry Co., Ltd., 19.5% colloidal silica dispersion) was heated to 60°C. Then, 15.5 g of (3-triethoxysilyl)propyl succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 60° C. for 4 hours to obtain an average secondary particle diameter of 60 nm in terms of volume. Aqueous dispersion B of cocoon-type silica particles surface-modified with carboxyl groups.
3.1.3. 水分散體C的製備 將甲醇70 g與3-胺基丙基三乙氧基矽烷(東京化成工業公司製造)11.3 g的混合液滴加至PL-3(扶桑化學工業公司製造,19.5%膠體二氧化矽分散液)2000 g中,在常壓下進行2小時回流。然後,一邊將容量保持固定一邊滴加純水,在塔頂溫度達到100℃的時刻結束純水的滴加,獲得包含體積換算下的平均二次粒徑56 nm的利用胺基進行了表面修飾的繭型的二氧化矽粒子的水分散體C。 3.1.3. Preparation of aqueous dispersion C A mixture of 70 g of methanol and 11.3 g of 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to PL-3 (manufactured by Fuso Chemical Industry Co., Ltd., 19.5% colloidal silica dispersion) 2000 g, under normal pressure for 2 hours reflux. Then, pure water was added dropwise while keeping the capacity constant, and the dropwise addition of pure water was stopped when the tower top temperature reached 100°C, and the surface-modified amine group was obtained including an average secondary particle diameter of 56 nm in terms of volume. Aqueous dispersion of cocoon-shaped silica particles C.
3.1.4. 水分散體D的製備 向PL-2L(扶桑化學工業公司製造,20%膠體二氧化矽分散液)1950 g中添加25%氨水(富士膠片和光純藥公司製造),調整為pH9。然後,滴加含(3-三乙氧基矽烷基)巰基的矽烷偶合劑(商品名「KBM-803」、信越化學工業公司製造)3.9 g,在60℃下攪拌2小時。然後,添加過氧化氫(富士膠片和光純藥公司製造)50 g,在常壓下回流8小時,獲得包含體積換算下的平均二次粒徑23 nm的利用磺基進行了表面修飾的球型二氧化矽粒子的水分散體D。 3.1.4. Preparation of aqueous dispersion D 25% ammonia water (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 1950 g of PL-2L (manufactured by Fuso Chemical Industry Co., Ltd., 20% colloidal silica dispersion) to adjust the pH to 9. Then, 3.9 g of a (3-triethoxysilyl)mercapto group-containing silane coupling agent (trade name "KBM-803", manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise, and stirred at 60° C. for 2 hours. Then, 50 g of hydrogen peroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and refluxed at normal pressure for 8 hours to obtain a spherical shape surface-modified with a sulfo group containing an average secondary particle diameter of 23 nm in terms of volume. Aqueous dispersion D of silica particles.
3.1.5. 水分散體E的製備 將PL-3(扶桑化學工業公司製造,19.5%膠體二氧化矽分散液)直接用作包含體積換算下的平均二次粒徑60 nm的未進行表面修飾的二氧化矽粒子的水分散體E。 3.1.5. Preparation of aqueous dispersion E PL-3 (manufactured by Fuso Chemical Industry Co., Ltd., 19.5% colloidal silica dispersion liquid) was directly used as the aqueous dispersion E containing non-surface-modified silica particles with an average secondary particle diameter of 60 nm in volume conversion .
3.1.6. 水分散體F的製備 向PL-1(扶桑化學工業公司製造,12%膠體二氧化矽分散液)3250 g中添加25%氨水(富士膠片和光純藥公司製造),調整為pH9。然後,滴加含(3-三乙氧基矽烷基)巰基的矽烷偶合劑(商品名「KBM-803」、信越化學工業公司製造)3.9 g,在60℃下攪拌2小時。然後,添加過氧化氫(富士膠片和光純藥公司製造)50 g,在常壓下回流8小時,獲得包含體積換算下的平均二次粒徑38 nm的利用磺基進行了表面修飾的二氧化矽粒子的水分散體F。 3.1.6. Preparation of aqueous dispersion F 25% ammonia water (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 3250 g of PL-1 (manufactured by Fuso Chemical Industry Co., Ltd., 12% colloidal silica dispersion) to adjust the pH to 9. Then, 3.9 g of a (3-triethoxysilyl)mercapto group-containing silane coupling agent (trade name "KBM-803", manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise, and stirred at 60° C. for 2 hours. Then, 50 g of hydrogen peroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and refluxed at normal pressure for 8 hours to obtain a hydrogen peroxide surface-modified with a sulfo group containing an average secondary particle diameter of 38 nm in terms of volume. Aqueous dispersion F of silicon particles.
3.1.7. 水分散體G的製備 按照日本專利特開2004-315300號公報中記載的實施例1製作二氧化矽粒子,獲得二氧化矽濃度為4質量%,體積換算下的平均二次粒徑7 nm的膠體二氧化矽粒子分散體。繼而,向所獲得的膠體二氧化矽粒子分散體6510 g中添加25%氨水(富士膠片和光純藥公司製造),調整為pH9。然後,滴加含(3-三乙氧基矽烷基)巰基的矽烷偶合劑(商品名「KBM-803」、信越化學工業公司製造)3.9 g,在60℃下攪拌2小時。然後,添加過氧化氫(富士膠片和光純藥公司製造)50 g,在常壓下回流8小時,獲得包含體積換算下的平均二次粒徑7 nm的利用磺基進行了表面修飾的二氧化矽粒子的水分散體G。 3.1.7. Preparation of aqueous dispersion G Silica particles were prepared according to Example 1 described in Japanese Patent Application Laid-Open No. 2004-315300 to obtain a colloidal silica particle dispersion with a silica concentration of 4% by mass and an average secondary particle diameter of 7 nm in volume conversion. body. Next, 25% ammonia water (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 6510 g of the obtained colloidal silica particle dispersion to adjust the pH to 9. Then, 3.9 g of a (3-triethoxysilyl)mercapto group-containing silane coupling agent (trade name "KBM-803", manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise, and stirred at 60° C. for 2 hours. Then, 50 g of hydrogen peroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and refluxed at normal pressure for 8 hours to obtain a hydrogen peroxide surface-modified with a sulfo group containing an average secondary particle diameter of 7 nm in terms of volume. Aqueous dispersion G of silicon particles.
3.1.8. 水分散體H的製備 按照國際公開第2008/072637號中記載的比較例1製作二氧化矽粒子,獲得二氧化矽濃度為29質量%,平均二次粒徑22 nm的二氧化矽粒子分散體。繼而,向所獲得的二氧化矽粒子分散體1350 g中添加25%氨水(富士膠片和光純藥公司製造),調整為pH9。然後,滴加含(3-三乙氧基矽烷基)巰基的矽烷偶合劑(商品名「KBM-803」、信越化學工業公司製造)3.9 g,在60℃下攪拌2小時。然後,添加過氧化氫(富士膠片和光純藥公司製造)50 g,在常壓下回流8小時,獲得包含體積換算下的平均二次粒徑23 nm的利用磺基進行了表面修飾的二氧化矽粒子的水分散體H。 3.1.8. Preparation of aqueous dispersion H Silica particles were produced according to Comparative Example 1 described in International Publication No. 2008/072637, and a silica particle dispersion with a silica concentration of 29% by mass and an average secondary particle diameter of 22 nm was obtained. Next, 25% ammonia water (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to 1350 g of the obtained silica particle dispersion to adjust the pH to 9. Then, 3.9 g of a (3-triethoxysilyl)mercapto group-containing silane coupling agent (trade name "KBM-803", manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise, and stirred at 60° C. for 2 hours. Then, 50 g of hydrogen peroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and refluxed at normal pressure for 8 hours to obtain a hydrogen peroxide surface-modified with a sulfo group containing an average secondary particle diameter of 23 nm in terms of volume. Aqueous dispersion H of silicon particles.
3.1.9. 水分散體I的製備 按照日本專利特開2004-315300號公報中記載的實施例1製作二氧化矽粒子,獲得二氧化矽濃度為4質量%,平均二次粒徑7 nm的膠體二氧化矽粒子分散體。然後,將所獲得的膠體二氧化矽粒子分散體6510 g加熱至60℃。然後,添加(3-三乙氧基矽烷基)丙基琥珀酸酐(東京化成工業公司製造)15.5 g,進而,在60℃下攪拌4小時,獲得包含體積換算下的平均二次粒徑7 nm的利用羧基進行了表面修飾的二氧化矽粒子的水分散體I。 3.1.9. Preparation of aqueous dispersion I Silica particles were prepared according to Example 1 described in Japanese Patent Application Laid-Open No. 2004-315300 to obtain a colloidal silica particle dispersion with a silica concentration of 4% by mass and an average secondary particle diameter of 7 nm. Then, 6510 g of the obtained colloidal silica particle dispersion was heated to 60°C. Then, 15.5 g of (3-triethoxysilyl)propyl succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirred at 60°C for 4 hours to obtain an average secondary particle diameter of 7 nm in terms of volume. Aqueous dispersion I of silica particles surface-modified with carboxyl groups.
3.2. 成分(D)的製備 3.2.1. 月桂基亞胺基二丙酸鹽的製備 將作為烷基胺的月桂基胺(東京化成工業公司製造)3.6 g(19.5 mmol)、3-氯丙酸(東京化學工業公司製造)5.7 g(52.9 mmol)加入至水5.0 mL、乙醇(關東化學公司製造)32 mL的混合溶液中,回流攪拌6小時。在所述回流攪拌中,加入由氫氧化鉀(關東化學公司製造)製備的氫氧化鉀水溶液(5.0 mol/L)7.8 mL,進行pH調整。然後,將溶液冷卻至4℃,生成沈澱物。將所生成的沈澱物利用乙醇進行洗淨後,進行過濾,並進行減壓乾燥而回收固體,獲得月桂基亞胺基二丙酸鹽。 3.2. Preparation of component (D) 3.2.1. Preparation of lauryl imino dipropionate Add 3.6 g (19.5 mmol) of laurylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.7 g (52.9 mmol) of 3-chloropropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) as an alkylamine to 5.0 mL of water, ethanol (Kanto Chemical Co., Ltd.) 32 mL of the mixed solution, reflux and stir for 6 hours. While stirring under reflux, 7.8 mL of an aqueous potassium hydroxide solution (5.0 mol/L) prepared from potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added to adjust the pH. Then, the solution was cooled to 4°C, and a precipitate formed. The generated precipitate was washed with ethanol, filtered, and dried under reduced pressure to recover a solid to obtain a lauryl imino dipropionate.
3.2.2. 肉豆蔻基亞胺基二丙酸鹽的製備 除了使用肉豆蔻胺(東京化成工業公司製造)4.2 g(19.5 mmol)作為烷基胺以外,進行與所述「3.2.1. 月桂基亞胺基二丙酸鹽的製備」同樣的操作,獲得肉豆蔻基亞胺基二丙酸鹽。 3.2.2. Preparation of myristyliminodipropionate Except for using 4.2 g (19.5 mmol) of myristylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as the alkylamine, the same operation as the above "3.2.1. Preparation of lauryl imino dipropionate" was carried out to obtain Myristyl imino dipropionate.
3.3. 化學機械研磨用組成物的製備 以成為表1~表5所示的組成的方式混合各成分,進而以成為表1~表5所示的pH的方式根據需要添加氫氧化鉀水溶液(關東化學公司製造,商品名「48%氫氧化鉀水溶液」)與磷酸(富士膠片和光純藥公司製造,商品名「磷酸」)或硝酸(關東化學公司製造,商品名「硝酸1.38」)而進行調整,以全部成分的合計量成為100質量%的方式添加純水,製備各實施例及各比較例的化學機械研磨用組成物。對於以所述方式獲得的各化學機械研磨用組成物,使用仄他電位測定裝置(美國分散技術公司(Dispersion Technology Inc.)製造,型號「DT300」)測定研磨粒的仄他電位,將測定結果一併示於表1~表5。 3.3. Preparation of composition for chemical mechanical polishing Each component was mixed so that the composition shown in Tables 1 to 5 was obtained, and an aqueous potassium hydroxide solution (manufactured by Kanto Chemical Co., Ltd., trade name "48% Hydrogen Potassium oxide aqueous solution") and phosphoric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "phosphoric acid") or nitric acid (manufactured by Kanto Chemical Co., Ltd., trade name "nitric acid 1.38"), adjusted so that the total amount of all components becomes 100 mass % of pure water was added to prepare the chemical mechanical polishing compositions of each embodiment and each comparative example. For each composition for chemical mechanical polishing obtained in the above manner, the zeta potential of the abrasive grains was measured using a zeta potential measuring device (manufactured by Dispersion Technology Inc., model "DT300"), and the measurement results were They are shown in Table 1 to Table 5 together.
3.4. 評價方法 3.4.1. 研磨速度評價 使用所述中所製備的化學機械研磨用組成物,將直徑12吋的帶釕膜100 nm的晶圓及直徑12吋的帶鉬膜500 nm的晶圓設為被研磨體,以下述的條件進行化學機械研磨試驗。 (研磨條件) ・研磨裝置:荏原製作所公司製造、型號「F-REX300SII」 ・研磨墊:杜邦(Dupont)公司製造,「多孔質聚胺基甲酸酯墊;光學(Optivision)9500 CMP 研磨墊(Polishing pad)」 ・化學機械研磨用組成物供給速度:250 mL/分 ・壓盤轉速:100 rpm ・研磨頭轉速:90 rpm ・研磨頭按壓壓力:2 psi ・研磨時間:60秒 ・研磨速度(nm/分)=(研磨前的膜的厚度(nm)-研磨後的膜的厚度(nm))/研磨時間(分) 3.4. Evaluation method 3.4.1. Grinding speed evaluation Using the composition for chemical mechanical polishing prepared in the above, a wafer with a diameter of 12 inches with a ruthenium film of 100 nm and a diameter with a diameter of 12 inches with a wafer with a molybdenum film of 500 nm are used as polished bodies, with the following conditions Carry out chemical mechanical grinding test. (grinding condition) ・Grinding device: Ebara Seisakusho Co., Ltd., model "F-REX300SII" ・Polishing pad: "Porous polyurethane pad; Optivision 9500 CMP polishing pad" manufactured by Dupont ・Chemical mechanical polishing composition supply rate: 250 mL/min ・Platen speed: 100 rpm ・Grinding head speed: 90 rpm ・Press pressure of grinding head: 2 psi ・Grinding time: 60 seconds ・Polishing speed (nm/min) = (film thickness before polishing (nm) - film thickness after polishing (nm))/polishing time (minutes)
再者,釕膜及鉬膜的厚度是藉由電阻率測定機(科磊(KLA-Tencor)公司製造,型號「RS-100」),以直流4探針法對電阻進行測定,並根據此片電阻值及釕的體積電阻率而由下述式算出。 ・釕膜的厚度(nm)=[釕膜的體積電阻率(Ω・m)÷片電阻值(Ω/sq)]×10 9・鉬膜的厚度(nm)=[鉬膜的體積電阻率(Ω・m)÷片電阻值(Ω/sq)]×10 9 Furthermore, the thickness of the ruthenium film and the molybdenum film is measured by the DC 4-probe method with a resistivity measuring machine (manufactured by KLA-Tencor, model "RS-100"), and according to this The sheet resistance value and the volume resistivity of ruthenium were calculated from the following equations.・Thickness of ruthenium film (nm) = [volume resistivity of ruthenium film (Ω・m) ÷ sheet resistance value (Ω/sq)] × 10 9・Thickness of molybdenum film (nm) = [volume resistivity of molybdenum film (Ω・m) ÷ chip resistance value (Ω/sq)]×10 9
釕膜的研磨速度的評價基準如下所述。將釕膜的研磨速度的評價結果一併示於表1~表3。 (評價基準) A:在研磨速度為100 nm/分以上的情況下,判斷為非常良好。 B:在研磨速度為50 nm/分以上且小於100 nm/分的情況下,可供於實用,因此判斷為良好。 C:在研磨速度小於50 nm/分的情況下,研磨速度小,難以實用,因此判斷為不良。 The evaluation criteria of the polishing rate of the ruthenium film are as follows. The evaluation results of the polishing rate of the ruthenium film are collectively shown in Tables 1 to 3. (evaluation criteria) A: When the polishing rate is 100 nm/min or more, it is judged to be very good. B: When the polishing rate is 50 nm/minute or more and less than 100 nm/minute, it can be used practically, so it was judged as good. C: When the polishing rate is less than 50 nm/min, the polishing rate is too small to be practical, so it was judged as defective.
鉬膜的研磨速度的評價基準如下所述。將鉬膜的研磨速度的評價結果一併示於表4~表5。 (評價基準) A:在研磨速度為100 nm/分以上的情況下,判斷為非常良好。 B:在研磨速度小於100 nm/分的情況下,研磨速度小,難以實用,因此判斷為不良。 The evaluation criteria of the polishing rate of the molybdenum film are as follows. The evaluation results of the polishing rate of the molybdenum film are collectively shown in Tables 4 to 5. (evaluation criteria) A: When the polishing rate is 100 nm/min or more, it is judged to be very good. B: When the polishing rate is less than 100 nm/min, the polishing rate is too small to be practical, so it was judged as defective.
3.4.2. 蝕刻速度評價 將所述中所製備的化學機械研磨用組成物升溫至60℃,將裁斷為30 mm×10 mm的帶釕膜100 nm的晶圓片或帶鉬膜200 nm的晶圓片浸漬5分鐘。然後,取出晶圓片,利用流水進行水洗,藉由與所述「3.3.1. 研磨速度評價」同樣的方法測定釕膜的厚度或鉬膜的厚度。然後,根據浸漬前後的釕膜的厚度或鉬膜的厚度的變化,利用下述式算出蝕刻速度。 ・釕膜的蝕刻速度(nm/分)=(蝕刻前的釕膜的厚度(nm)-蝕刻後的釕膜的厚度(nm))/蝕刻時間(分) ・鉬膜的蝕刻速度(nm/分)=(蝕刻前的鉬膜的厚度(nm)-蝕刻後的鉬膜的厚度(nm))/蝕刻時間(分) 3.4.2. Etching rate evaluation The chemical mechanical polishing composition prepared above was heated to 60° C., and a wafer with a ruthenium film of 100 nm or a wafer with a molybdenum film of 200 nm cut into a size of 30 mm×10 mm was immersed for 5 minutes. Then, the wafer was taken out, washed with running water, and the thickness of the ruthenium film or the thickness of the molybdenum film was measured by the same method as the above-mentioned "3.3.1. Polishing rate evaluation". Then, the etching rate was calculated by the following formula from the change in the thickness of the ruthenium film or the thickness of the molybdenum film before and after immersion. ・Etching rate of ruthenium film (nm/min) = (thickness of ruthenium film before etching (nm) - thickness of ruthenium film after etching (nm))/etching time (min) ・Etching rate of molybdenum film (nm/min) = (thickness of molybdenum film before etching (nm) - thickness of molybdenum film after etching (nm))/etching time (min)
釕膜的蝕刻速度的評價基準如下所述。將釕膜的蝕刻速度的評價結果一併示於表1~表3。 (評價基準) A:在蝕刻速度小於1.5 nm/分的情況下,判斷為非常良好。 B:在蝕刻速度為1.5 nm/分以上且小於3 nm/分的情況下,可供於實用,因此判斷為良好。 C:在蝕刻速度為3 nm/分以上的情況下,蝕刻速度大,難以實用,因此判斷為不良。 The evaluation criteria of the etching rate of the ruthenium film are as follows. The evaluation results of the etching rate of the ruthenium film are collectively shown in Tables 1 to 3. (evaluation criteria) A: When the etching rate is less than 1.5 nm/min, it is judged to be very good. B: When the etching rate is not less than 1.5 nm/min and less than 3 nm/min, it can be used for practical use, so it was judged to be good. C: When the etching rate is 3 nm/min or more, the etching rate is too high to be practical, so it was judged as defective.
鉬膜的蝕刻速度的評價基準如下所述。將鉬膜的蝕刻速度的評價結果一併示於表4~表5。 (評價基準) A:在蝕刻速度小於20 nm/分的情況下,判斷為非常良好。 B:在蝕刻速度為20 nm/分以上的情況下,蝕刻速度大,難以實用,因此判斷為不良。 The evaluation criteria of the etching rate of the molybdenum film are as follows. The evaluation results of the etching rate of the molybdenum film are collectively shown in Tables 4 to 5. (evaluation criteria) A: When the etching rate is less than 20 nm/min, it is judged to be very good. B: When the etching rate is 20 nm/min or more, the etching rate is too high to be practical, so it was judged as defective.
3.4.3.貯存穩定性評價 將所述中所製備的化學機械研磨用組成物在20℃的恆溫保管庫中保管3天或7天後,將直徑12吋的帶釕膜100 nm的晶圓或直徑12吋的帶鉬膜500 nm的晶圓設為被研磨體,在與所述「3.4.1. 研磨速度評價」相同的研磨條件下進行化學機械研磨試驗。然後,藉由下述式算出保管前後的釕膜的研磨速度的變動率。 變動率(%)=|((「3.4.1. 研磨速度評價」項中算出的研磨速度)-(使用保管後的化學機械研磨用組成物時的研磨速度))/(「3.4.1. 研磨速度評價」項中算出的研磨速度)×100| 3.4.3. Storage stability evaluation After the composition for chemical mechanical polishing prepared in the above was stored in a constant temperature storage room at 20°C for 3 days or 7 days, a 12-inch diameter wafer with a ruthenium film of 100 nm or a diameter of 12 inches with a molybdenum film A 500 nm wafer was used as the object to be polished, and a chemical mechanical polishing test was performed under the same polishing conditions as described in "3.4.1. Polishing rate evaluation". Then, the variation rate of the polishing rate of the ruthenium film before and after storage was calculated by the following formula. Variation rate (%)=|((Polishing rate calculated in "3.4.1. Polishing rate evaluation" item) - (Polishing rate when using the chemical mechanical polishing composition after storage))/("3.4.1. Grinding speed calculated in "Grinding speed evaluation" item) × 100|
變動率的評價基準如下所述。將化學機械研磨用組成物的貯存穩定性的評價結果一併示於表1~表5。 (評價基準) A:在貯存後經過7天時的研磨速度的變動率小於10%的情況下,判斷為非常良好。 B:在貯存後經過3天時的研磨速度的變動率小於10%,但貯存後經過7天時的研磨速度的變動率為10%以上的情況下,可供於實用,因此判斷為良好。 C:在貯存後經過3天時的研磨速度的變動率為10%以上的情況下,由於難以實用,因此判斷為不良。 The evaluation criteria of the rate of change are as follows. The evaluation results of the storage stability of the chemical mechanical polishing composition are collectively shown in Tables 1 to 5. (evaluation criteria) A: When the fluctuation rate of the polishing rate after 7 days of storage is less than 10%, it is judged to be very good. B: The variation rate of the polishing rate after 3 days of storage is less than 10%, but the rate of variation of the polishing rate after 7 days of storage is 10% or more, so it can be used for practical use, so it is judged as good. C: When the variation rate of the polishing rate after 3 days of storage was 10% or more, it was judged as defective because it was difficult to put into practical use.
3.5. 評價結果 表1~表5中示出各實施例及各比較例中使用的化學機械研磨用組成物的組成以及各評價結果。 3.5. Evaluation Results Tables 1 to 5 show the composition of the chemical mechanical polishing composition used in each of the Examples and each of the Comparative Examples and each of the evaluation results.
[表1]
[表2]
[表3]
[表4]
[表5]
上表1~上表5中的各成分分別使用下述商品或試劑。 <成分(A)> ・水分散體A~水分散體I:所述「3.1.二氧化硅粒子水分散體的製備」項中製備的水分散體A~水分散體I <成分(D)> ・N-(膦醯基甲基)亞胺基二乙酸:西格瑪奧瑞奇公司(Sigma-Aldrich)公司製造,商品名「N-(膦醯基甲基)亞胺基二乙酸 水合物」 ・羥乙基亞胺基二乙酸:東京化成工業公司製造,商品名「N-(2-羥乙基)亞胺基二乙酸(N-(2-Hydroxyethyl)iminodiacetic Acid)」 ・N-(2-羧乙基)亞胺基二乙酸:東京化成工業公司製造,商品名「N-(2-羧乙基)亞胺基二乙酸(N-(2-Carboxyethyl)iminodiacetic Acid)」 ・氮基三乙酸:東京化成工業公司製造,商品名「氮基三乙酸(Nitrilotriacetic Acid)」 ・3,3',3"-氮基三丙酸:東京化成工業公司製造,商品名「3,3',3"-氮基三丙酸(3,3',3"-Nitrilopropionic Acid)」 ・乙二胺四乙酸:東京化成工業公司製造,商品名「乙二胺四乙酸(Ethylenediaminetetraacetic Acid)」 ・月桂基亞胺基二丙酸鹽:在所述「3.2. 成分(D)的製備」項中製備的月桂基亞胺基二丙酸鹽 ・肉豆蔻基亞胺基二丙酸鹽:在所述「3.2. 成分(D)的製備」項中製備的肉豆蔻基亞胺基二丙酸鹽 ・十二烷基胺基乙基胺基乙基甘胺酸:三洋化成工業公司製造,商品名「萊伯(Rebon) S」 <成分(B)> ・H 5IO 6(過碘酸):富士膠片和光純藥公司製造,商品名「原過碘酸」 ・KClO(次氯酸鉀):關東化學公司製造,商品名「次氯酸鉀溶液」 ・KClO 2(亞氯酸鉀):安寢(Angene)公司製造,商品名「亞氯酸鉀(Potassium Chlorite)」 ・NaBrO(次溴酸鈉):關東化學公司製造,商品名「次溴酸鈉」 <成分(C)> ・過氧化氫:富士膠片和光純藥公司製造,30%水溶液 <其他成分> ・2-膦醯基丁烷-1,2,4-三羧酸:東京化成工業公司製造,商品名「2-膦醯基丁烷-1,2,4-三羧酸(2-Phosphonobutane-1,2,4-tricarboxylic Acid)(約50%水溶液(ca. 50% in Water))」 ・N,N,N',N'-四甲基乙二胺:東京化成工業公司製造,商品名「N,N,N',N'-四甲基乙二胺(N,N,N',N'-Tetramethylethylenediamine)」 ・1-羥基亞乙基-1,1-二膦酸:東京化成工業公司製造,商品名「1-羥基亞乙基-1,1-二膦酸(1-Hydroxyethane-1,1-diphosphonic Acid)(約60%水溶液,約4.2 mol/L(ca. 60% in Water, ca. 4.2 mol/L))」 ・乙二胺四(亞甲基膦酸):東京化成工業公司製造,商品名「N,N,N',N'-乙二胺四(亞甲基膦酸)(N,N,N',N'-Ethylenediaminetetrakis(methylenephosphonic Acid))」 ・丙二酸:東京化成工業公司製造,商品名「Malonic Acid」 ・鄰苯二甲酸:東京化成工業公司製造,商品名「Phthalic Acid」 ・檸檬酸:東京化成工業公司製造,商品名「Citric Acid」 ・己二酸:東京化成工業公司製造,商品名「Adipic Acid」 ・L-酒石酸:東京化成工業公司製造,商品名「L-(+)-Tartaric Acid」 ・硝酸鐵九水合物,富士膠片和光純藥公司製造,商品名「硝酸鐵(III)九水合物」 ・檸檬酸鐵水合物,富士膠片和光純藥公司製造,商品名「檸檬酸鐵(III)n水合物」 ・乙醯丙酮鐵,東京化成工業公司製造,商品名「三(2,4-戊二酮)合鐵(Tris(2,4-pentanedionato)iron)(III)」 ・乙基三甲基氫氧化銨,三開化工(SACHEM)公司製造,商品名「Envure SE TM3330」 ・苄基三甲基氫氧化銨,東京化成工業公司製造,商品名「Benzyltrimethylammonium Hydroxide (40%水溶液(40% in Water))」 ・三甲基金剛烷基氫氧化銨,東京化成工業公司製造,商品名「N,N,N-三甲基-1-金剛烷基氫氧化銨(N,N,N-Trimethyl-1-adamantylammonium Hydroxide)(25%水溶液(25% in Water))」 ・四乙基氫氧化銨,東京化成工業公司製造,商品名「Tetra ethylammonium Hydroxide (10%水溶液(10% in Water))」 ・四丁基氫氧化銨,東京化成工業公司製造,商品名「Tetrabutylammonium Hydroxide(40%水溶液(40% in Water))」 For each component in the above Table 1 to the above Table 5, the following commercial products or reagents were used, respectively. <Component (A)> ・Water dispersion A to water dispersion I: Water dispersion A to water dispersion I prepared in the section "3.1. Preparation of aqueous silica particle dispersion" above <Component (D) > ・N-(phosphonomethyl)iminodiacetic acid: manufactured by Sigma-Aldrich, trade name "N-(phosphonomethyl)iminodiacetic acid hydrate"・Hydroxyethyliminodiacetic acid: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "N-(2-Hydroxyethyl)iminodiacetic Acid (N-(2-Hydroxyethyl)iminodiacetic Acid)" ・N-(2 -Carboxyethyl)iminodiacetic acid: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "N-(2-Carboxyethyl)iminodiacetic Acid (N-(2-Carboxyethyl)iminodiacetic Acid)" Acetic acid: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Nitrilotriacetic Acid""-Nitrilopropionic Acid (3,3',3"-Nitrilopropionic Acid)" ・Ethylenediaminetetraacetic acid: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Ethylenediaminetetraacetic Acid (Ethylenediaminetetraacetic Acid)" ・Lauryl Aminodipropionate: lauryl imino dipropionate prepared in the item "3.2. Preparation of component (D)" above. Myristyl imino dipropionate: . Myristyl iminodipropionate and dodecylaminoethylaminoethylglycine prepared in "Preparation of Component (D)": manufactured by Sanyo Chemical Industry Co., Ltd., trade name "Leber (Rebon) S"<Component(B)> ・H 5 IO 6 (periodic acid): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "orthoperiodic acid" ・KClO (potassium hypochlorite): manufactured by Kanto Chemical Co., Ltd. Trade name "potassium hypochlorite solution" ・KClO 2 (potassium chlorite): manufactured by Angene Corporation, trade name "Potassium Chlorite" ・NaBrO (sodium hypobromite): manufactured by Kanto Chemical Co., Ltd., trade name " Sodium hypobromite"<Ingredient(C)> ・Hydrogen peroxide: Fujifilm Wako Pure Chemical Industries, Ltd., 30% aqueous solution <Other ingredients> ・2-phosphonobutane-1,2,4-tricarboxylic acid: Tokyo Chemical Industry Co., Ltd., trade name "2-Phosphonobutane-1,2,4-tricarboxylic acid (2-Phosphonobutane-1,2,4-tricarboxylic Acid) (about 50% aqueous solution (ca. 50% in Water))"・N,N,N',N'-tetramethylethylenediamine: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "N,N,N',N'-tetramethylethylenediamine (N ,N,N',N'-Tetramethylethylenediamine)" ・1-Hydroxyethylene-1,1-diphosphonic acid: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "1-hydroxyethylene-1,1-diphosphine Acid (1-Hydroxyethane-1,1-diphosphonic Acid) (about 60% aqueous solution, about 4.2 mol/L (ca. 60% in Water, ca. 4.2 mol/L))”・Ethylenediaminetetra(methylene Phosphonic acid): manufactured by Tokyo Chemical Industry Co., Ltd., trade name "N,N,N',N'-ethylenediaminetetrakis (methylenephosphonic acid) (N,N,N',N'-Ethylenediaminetetrakis (methylenephosphonic Acid) )" ・Malonic acid: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Malonic Acid" ・Phthalic acid: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Phthalic Acid" Citric Acid" ・Adipic acid: Tokyo Chemical Industry Co., Ltd., trade name "Adipic Acid" ・L-Tartaric acid: Tokyo Chemical Industry Co., Ltd., trade name "L-(+)-Tartaric Acid" Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "iron (III) nitrate nonahydrate" ・Ferric citrate hydrate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "iron (III) citrate n-hydrate" ・B Iron acetonate, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Tris(2,4-pentanedionato)iron (III)" ・Ethyltrimethylammonium hydroxide, SACHEM Co., Ltd., trade name "Envure SE TM 3330" ・Benzyltrimethylammonium hydroxide, Tokyo Chemical Industry Co., Ltd., trade name "Benzyltrimethylammonium Hydroxide (40% aqueous solution (40% in Water))"・Trimethyladamantylammonium hydroxide, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "N,N,N-Trimethyl-1-adamantylammonium hydroxide (N,N,N-Trimethyl-1-adamantylammonium Hydroxide) (25% aqueous solution (25% in Water))" ・Tetraethylammonium hydroxide, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Tetra ethylammonium Hydroxide (10% aqueous solution (10% in Water))" ・Tetrabutyl Ammonium hydroxide, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Tetrabutylammonium Hydroxide (40% aqueous solution (40% in Water))"
根據併用了具有特定官能基的成分(A)與成分(D)的實施例1~實施例23的化學機械研磨用組成物,可知,藉由使成分(A)容易吸附在釕膜或鉬膜上,可提高釕膜或鉬膜的研磨速度,並且藉由使成分(D)吸附在釕膜或鉬膜的表面而形成保護膜,可抑制釕膜或鉬膜的過度腐蝕。另外可知,藉由使用具有特定官能基的成分(A),化學機械研磨用組成物中的研磨粒之間的排斥力提高,研磨粒的凝聚得到抑制,因此貯存穩定性提高。According to the chemical mechanical polishing compositions of Examples 1 to 23 in which component (A) and component (D) having a specific functional group are used in combination, it can be seen that by making component (A) easily adsorbed on a ruthenium film or a molybdenum film On the other hand, the polishing rate of the ruthenium film or the molybdenum film can be increased, and the excessive corrosion of the ruthenium film or the molybdenum film can be suppressed by forming a protective film by adsorbing the component (D) on the surface of the ruthenium film or the molybdenum film. In addition, it was found that by using the component (A) having a specific functional group, the repulsive force between the abrasive grains in the chemical mechanical polishing composition is improved, the aggregation of the abrasive grains is suppressed, and thus the storage stability is improved.
與此相對,根據含有不具有特定官能基的研磨粒的比較例1~比較例2、比較例8~比較例12的化學機械研磨用組成物,可知釕膜或鉬膜的研磨速度降低,難以供於實用。另外可知,根據使用了成分(D)的替代成分的比較例3~比較例7的化學機械研磨用組成物,在研磨對象為釕膜的情況下,無法抑制釕膜的腐蝕,或者有時亦可在某種程度上抑制釕膜的腐蝕,但由於該成分與特定陰離子種反應,貯存穩定性顯著惡化,難以供於實用。進而可知,根據不含有成分(D)的比較例10~比較例14的化學機械研磨用組成物,在研磨對象為鉬膜的情況下,鉬膜的研磨速度顯著降低。On the other hand, according to the compositions for chemical mechanical polishing of Comparative Examples 1 to 2 and Comparative Examples 8 to 12 containing abrasive grains that do not have a specific functional group, it can be seen that the polishing speed of the ruthenium film or the molybdenum film is reduced, and it is difficult to For practical use. In addition, it can be seen that according to the chemical mechanical polishing compositions of Comparative Examples 3 to 7 using alternative components of component (D), when the polishing object is a ruthenium film, the corrosion of the ruthenium film cannot be suppressed, or sometimes Corrosion of the ruthenium film can be suppressed to some extent, but since this component reacts with a specific anion species, the storage stability is significantly deteriorated, and it is difficult to be used for practical use. Furthermore, according to the chemical mechanical polishing compositions of Comparative Examples 10 to 14 not containing the component (D), when the polishing object is a molybdenum film, the polishing rate of the molybdenum film is significantly reduced.
本發明並不限定於所述實施方式,能夠進行各種變形。例如,本發明包括與實施方式中所說明的結構實質上相同的結構(例如功能、方法及結果相同的結構、或者目的及效果相同的結構)。另外,本發明包括對實施方式中所說明的結構的非本質部分進行替換而成的結構。另外,本發明包括發揮與實施方式中所說明的結構相同的作用效果的結構或可達成相同目的的結構。另外,本發明包括對實施方式中所說明的結構附加公知技術所得的結構。The present invention is not limited to the above-described embodiments, and various modifications are possible. For example, the present invention includes structures substantially the same as those described in the embodiments (for example, structures having the same functions, methods, and results, or structures having the same purpose and effects). In addition, this invention includes the structure which replaced the non-essential part of the structure demonstrated in embodiment. In addition, the present invention includes configurations that exhibit the same effects as the configurations described in the embodiments, or configurations that can achieve the same purpose. In addition, the present invention includes structures obtained by adding known techniques to the structures described in the embodiments.
10:基體 12:氧化矽膜 14:配線用槽 16:含釕的膜 18:銅膜 42:漿料供給噴嘴 44:漿料(化學機械研磨用組成物) 46:研磨用墊 48:轉盤 50:半導體基板 52:載架頭 54:水供給噴嘴 56:修整器 100:被處理體 200:研磨裝置 10: matrix 12: Silicon oxide film 14: Groove for wiring 16: Membrane containing ruthenium 18: copper film 42: Slurry supply nozzle 44: Slurry (composition for chemical mechanical polishing) 46: Grinding pad 48: turntable 50:Semiconductor substrate 52: carrier head 54: Water supply nozzle 56: Dresser 100: object to be processed 200: grinding device
圖1是示意性地表示適合在本實施方式的研磨步驟中使用的被處理體的剖面圖。 圖2是示意性地表示第一研磨步驟結束時的被處理體的剖面圖。 圖3是示意性地表示第二研磨步驟結束時的被處理體的剖面圖。 圖4是示意地表示化學機械研磨裝置的立體圖。 FIG. 1 is a schematic cross-sectional view of an object to be processed that is suitable for use in the polishing step of the present embodiment. Fig. 2 is a cross-sectional view schematically showing the object to be processed at the end of the first polishing step. Fig. 3 is a cross-sectional view schematically showing the object to be processed at the end of the second polishing step. Fig. 4 is a perspective view schematically showing a chemical mechanical polishing device.
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