JPWO2021095413A1 - Composition for chemical mechanical polishing and chemical mechanical polishing method - Google Patents
Composition for chemical mechanical polishing and chemical mechanical polishing method Download PDFInfo
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- JPWO2021095413A1 JPWO2021095413A1 JP2021502914A JP2021502914A JPWO2021095413A1 JP WO2021095413 A1 JPWO2021095413 A1 JP WO2021095413A1 JP 2021502914 A JP2021502914 A JP 2021502914A JP 2021502914 A JP2021502914 A JP 2021502914A JP WO2021095413 A1 JPWO2021095413 A1 JP WO2021095413A1
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- Prior art keywords
- chemical mechanical
- mechanical polishing
- ether
- composition
- mass
- Prior art date
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- 239000000126 substance Substances 0.000 title claims abstract description 139
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- 238000000034 method Methods 0.000 title claims abstract description 31
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- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 30
- 239000010937 tungsten Substances 0.000 claims abstract description 30
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- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- 125000001033 ether group Chemical group 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 19
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- 150000007524 organic acids Chemical class 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
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- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 4
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- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 4
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- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- NIONDZDPPYHYKY-UHFFFAOYSA-N Z-hexenoic acid Natural products CCCC=CC(O)=O NIONDZDPPYHYKY-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- MXJIHEXYGRXHGP-UHFFFAOYSA-N benzotriazol-1-ylmethanol Chemical compound C1=CC=C2N(CO)N=NC2=C1 MXJIHEXYGRXHGP-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- KVUDZUPUUSUAAJ-UHFFFAOYSA-N bis(chloromethyl) carbonate Chemical compound ClCOC(=O)OCCl KVUDZUPUUSUAAJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- QBEGYEWDTSUVHH-UHFFFAOYSA-P diazanium;cerium(3+);pentanitrate Chemical compound [NH4+].[NH4+].[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBEGYEWDTSUVHH-UHFFFAOYSA-P 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 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
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 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
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000011163 secondary particle Substances 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
- 239000000344 soap Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 150000003657 tungsten Chemical class 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)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Silicon Compounds (AREA)
Abstract
タングステンやコバルト等の導電体金属を含む半導体基板を高速かつ平坦に研磨することができるとともに、研磨後の表面欠陥を低減できる化学機械研磨組成物、及び化学機械研磨方法を提供する。本発明に係る化学機械研磨用組成物は、（Ａ）下記一般式（１）で表される官能基を有するシリカ粒子と、（Ｂ）水酸基及びエーテル基を有する化合物と、を含有する。−ＣＯＯ−Ｍ＋・・・・・（１）（Ｍ＋は１価の陽イオンを表す。）Provided are a chemical mechanical polishing composition capable of polishing a semiconductor substrate containing a conductive metal such as tungsten or cobalt at high speed and flatly, and reducing surface defects after polishing, and a chemical mechanical polishing method. The composition for chemical mechanical polishing according to the present invention contains (A) silica particles having a functional group represented by the following general formula (1), and (B) a compound having a hydroxyl group and an ether group. -COO-M + ... (1) (M + represents a monovalent cation.)
Description
本発明は、化学機械研磨用組成物及び化学研磨方法に関する。 The present invention relates to a composition for chemical mechanical polishing and a chemical polishing method.
半導体装置内に形成される配線及びプラグ等からなる配線層の微細化が進んでいる。これに伴い、配線層を化学機械研磨（以下、「ＣＭＰ」ともいう。）により平坦化する手法が用いられている。このようなＣＭＰの最終的な目的は、研磨後に、被研磨面を平坦化し、無欠陥かつ無腐食の表面を得ることである。そのため、ＣＭＰで使用される化学機械研磨用組成物は、材料除去速度、研磨後の表面欠陥品率、及び研磨後の金属腐食防止等の特性により評価される。 The miniaturization of the wiring layer composed of wiring, plugs, etc. formed in the semiconductor device is progressing. Along with this, a method of flattening the wiring layer by chemical mechanical polishing (hereinafter, also referred to as “CMP”) has been used. The ultimate purpose of such a CMP is to flatten the surface to be polished after polishing to obtain a defect-free and corrosion-free surface. Therefore, the chemical mechanical polishing composition used in CMP is evaluated based on characteristics such as material removal rate, surface defect product rate after polishing, and metal corrosion prevention after polishing.
近年、配線層の更なる微細化により、導電体金属としてタングステン（Ｗ）やコバルト（Ｃｏ）が適用され始めている。そのため、余剰に積層されたタングステンやコバルトをＣＭＰにより効率的に除去しつつ、かつ、タングステンやコバルトの腐食を抑制し、良好な表面状態を形成できることが要求されている。このようなタングステンやコバルトの化学機械研磨に関し、種々の添加剤を含有する化学機械研磨用組成物が提案されている（例えば、特許文献１及び特許文献２参照）。 In recent years, due to further miniaturization of wiring layers, tungsten (W) and cobalt (Co) have begun to be applied as conductor metals. Therefore, it is required that the excessively laminated tungsten and cobalt can be efficiently removed by CMP, and the corrosion of tungsten and cobalt can be suppressed to form a good surface state. Regarding such chemical mechanical polishing of tungsten and cobalt, a composition for chemical mechanical polishing containing various additives has been proposed (see, for example, Patent Document 1 and Patent Document 2).
タングステンやコバルト等の導電体金属を含む半導体ウエハの普及に伴い、タングステンやコバルト等の導電体金属を含む半導体基板を高速かつ平坦に研磨することができるとともに、研磨後の表面欠陥を低減できる化学機械研磨用組成物、及び化学機械研磨方法が要求されている。 With the widespread use of semiconductor wafers containing conductive metals such as tungsten and cobalt, semiconductor substrates containing conductive metals such as tungsten and cobalt can be polished at high speed and flatly, and surface defects after polishing can be reduced. A composition for mechanical polishing and a chemical mechanical polishing method are required.
本発明に係る化学機械研磨用組成物の一態様は、
（Ａ）下記一般式（１）で表される官能基を有するシリカ粒子と、
（Ｂ）水酸基及びエーテル基を有する化合物と、
を含有する。
−ＣＯＯ−Ｍ＋ ・・・・・（１）
（Ｍ＋は１価の陽イオンを表す。）One aspect of the chemical mechanical polishing composition according to the present invention is
(A) Silica particles having a functional group represented by the following general formula (1) and
(B) A compound having a hydroxyl group and an ether group, and
Contains.
-COO - M + ... (1)
(M + represents a monovalent cation.)
前記化学機械研磨用組成物の一態様において、
化学機械研磨用組成物の全質量を１００質量％としたときに、
前記（Ａ）成分の含有量が０．１質量％以上１０質量％以下であり、
前記（Ｂ）成分の含有量が０．０００１質量％以上０．０５質量％以下であることができる。In one aspect of the chemical mechanical polishing composition,
When the total mass of the chemical mechanical polishing composition is 100% by mass,
The content of the component (A) is 0.1% by mass or more and 10% by mass or less.
The content of the component (B) can be 0.0001% by mass or more and 0.05% by mass or less.
前記化学機械研磨用組成物のいずれかの態様において、
前記（Ａ）成分は、その表面に前記一般式（１）で表される官能基が共有結合を介して固定されたシリカ粒子であることができる。In any aspect of the chemical mechanical polishing composition.
The component (A) can be silica particles in which the functional group represented by the general formula (1) is fixed on the surface thereof via a covalent bond.
前記化学機械研磨用組成物のいずれかの態様において、
前記（Ｂ）成分が、標準沸点が８０℃以上のグリコールエーテルであることができる。In any aspect of the chemical mechanical polishing composition.
The component (B) can be a glycol ether having a standard boiling point of 80 ° C. or higher.
前記化学機械研磨用組成物のいずれかの態様において、
前記（Ｂ）成分が、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノアリルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、３−メトキシ−３−メチル−１−ブタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノベンジルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノプロピルエーテル、トリエチレングリコールモノブチルエーテル及びトリプロピレングリコールモノブチルエーテルから選択される１種以上であることができる。In any aspect of the chemical mechanical polishing composition.
The component (B) is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoallyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl. Ether, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, dipropylene glycol monomethyl ether, dipropylene From Glycol Monoethyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monobutyl Ether, Triethylene Glycol Monomethyl Ether, Triethylene Glycol Monoethyl Ether, Triethylene Glycol Monopropyl Ether, Triethylene Glycol Monobutyl Ether and Tripropylene Glycol Monobutyl Ether It can be one or more selected.
前記化学機械研磨用組成物のいずれかの態様において、
さらに、有機酸を含有することができる。In any aspect of the chemical mechanical polishing composition.
In addition, it can contain organic acids.
前記化学機械研磨用組成物のいずれかの態様において、
さらに、酸化剤を含有することができる。In any aspect of the chemical mechanical polishing composition.
In addition, it can contain an oxidizing agent.
前記化学機械研磨用組成物のいずれかの態様において、
ｐＨが２以上５以下であることができる。In any aspect of the chemical mechanical polishing composition.
The pH can be 2 or more and 5 or less.
本発明に係る化学機械研磨方法の一態様は、
前記いずれかの態様の化学機械研磨用組成物を用いて半導体基板を研磨する工程を含む。One aspect of the chemical mechanical polishing method according to the present invention is
The step of polishing a semiconductor substrate with the composition for chemical mechanical polishing according to any one of the above is included.
前記化学機械研磨方法の一態様において、
前記半導体基板が、酸化シリコン及びタングステンよりなる群から選択される少なくとも１種を含有する部位を備えることができる。In one aspect of the chemical mechanical polishing method
The semiconductor substrate may include a moiety containing at least one selected from the group consisting of silicon oxide and tungsten.
本発明に係る化学機械研磨用組成物によれば、タングステンやコバルト等の導電体金属を含む半導体基板を高速かつ平坦に研磨することができるとともに、研磨後の表面欠陥を低減することができる。 According to the chemical mechanical polishing composition according to the present invention, a semiconductor substrate containing a conductor metal such as tungsten or cobalt can be polished at high speed and flatly, and surface defects after polishing can be reduced.
以下、本発明の好適な実施形態について詳細に説明する。なお、本発明は、下記の実施形態に限定されるものではなく、本発明の要旨を変更しない範囲において実施される各種の変形例も含む。 Hereinafter, preferred embodiments of the present invention will be described in detail. It should be noted that the present invention is not limited to the following embodiments, and includes various modifications implemented without changing the gist of the present invention.
本明細書において、「Ｘ〜Ｙ」を用いて記載された数値範囲は、数値Ｘを下限値として含み、かつ、数値Ｙを上限値として含むものとして解釈される。 In the present specification, the numerical range described by using "X to Y" is interpreted as including the numerical value X as the lower limit value and the numerical value Y as the upper limit value.
１．化学機械研磨用組成物
本発明の一実施形態に係る化学機械研磨用組成物は、（Ａ）下記一般式（１）で表される官能基を有するシリカ粒子（本明細書において、単に「（Ａ）成分」ともいう。）と、（Ｂ）水酸基及びエーテル基を有する化合物（本明細書において、単に「（Ｂ）成分」ともいう。）と、を含有する。
−ＣＯＯ−Ｍ＋ ・・・・・（１）
（Ｍ＋は１価の陽イオンを表す。）
以下、本実施形態に係る化学機械研磨用組成物に含まれる各成分について詳細に説明する。1. 1. Composition for Chemical Mechanical Polishing The composition for chemical mechanical polishing according to an embodiment of the present invention is (A) silica particles having a functional group represented by the following general formula (1) (in the present specification, simply "((in this specification)". It also contains "A) component") and (B) a compound having a hydroxyl group and an ether group (also simply referred to as "(B) component" in the present specification).
-COO - M + ... (1)
(M + represents a monovalent cation.)
Hereinafter, each component contained in the chemical mechanical polishing composition according to the present embodiment will be described in detail.
１．１．（Ａ）成分
本実施形態に係る化学機械研磨用組成物は、砥粒成分として、（Ａ）下記一般式（１）で表される官能基を有するシリカ粒子を含有する。
−ＣＯＯ−Ｍ＋ ・・・・・（１）
（Ｍ＋は１価の陽イオンを表す。）
Ｍ＋で表される１価の陽イオンとしては、これらに限定されないが、例えば、Ｈ＋、Ｌｉ＋、Ｎａ＋、Ｋ＋、ＮＨ４ ＋が挙げられる。すなわち、（Ａ）成分は、「（Ａ）カルボキシ基及びその塩よりなる群から選択される少なくとも１種の官能基を有するシリカ粒子」と言い換えることもできる。ここで、「カルボキシ基の塩」とは、カルボキシ基（−ＣＯＯＨ）に含まれている水素イオンをＬｉ＋、Ｎａ＋、Ｋ＋、ＮＨ４ ＋等の１価の陽イオンで置換した官能基のことをいう。（Ａ）成分は、その表面に上記一般式（１）で表される官能基が共有結合を介して固定されたシリカ粒子であり、その表面に上記一般式（１）で表される官能基を有する化合物が物理的あるいはイオン的に吸着したようなものは含まれない。1.1. (A) Component The chemical mechanical polishing composition according to the present embodiment contains (A) silica particles having a functional group represented by the following general formula (1) as an abrasive grain component.
-COO - M + ... (1)
(M + represents a monovalent cation.)
Examples of the monovalent cation represented by M +, but not limited to, for example, H +, Li +, Na +, K +, include NH 4 +. That is, the component (A) can be rephrased as "silica particles having at least one functional group selected from the group consisting of (A) a carboxy group and a salt thereof". Here, the "salt of a carboxy group" is a functional group in which a hydrogen ion contained in a carboxy group (-COOH) is replaced with a monovalent cation such as Li + , Na + , K + , NH 4 + or the like. It means that. The component (A) is a silica particle in which a functional group represented by the general formula (1) is fixed on the surface thereof via a covalent bond, and the functional group represented by the general formula (1) is fixed on the surface thereof. It does not include those in which the compound having the above is physically or ionically adsorbed.
本実施形態において使用される（Ａ）成分は、例えば、以下のようにして製造することができる。
まず、シリカ粒子を用意する。シリカ粒子としては、例えば、ヒュームドシリカ、コロイダルシリカ等が挙げられるが、スクラッチ等の研磨欠陥を低減する観点から、コロイダルシリカが好ましい。コロイダルシリカは、例えば、特開２００３−１０９９２１号公報等に記載された方法で製造されたものを使用することができる。このようなシリカ粒子の表面を修飾することにより、本実施形態で使用可能な（Ａ）成分を製造することができる。以下にシリカ粒子の表面を修飾する方法を例示するが、本発明はこの具体例により何ら限定されるものではない。The component (A) used in the present embodiment can be produced, for example, as follows.
First, silica particles are prepared. Examples of the silica particles include fumed silica and colloidal silica, but colloidal silica is preferable from the viewpoint of reducing polishing defects such as scratches. As the colloidal silica, for example, those manufactured by the method described in JP-A-2003-109921 can be used. By modifying the surface of such silica particles, the component (A) that can be used in the present embodiment can be produced. Hereinafter, a method for modifying the surface of silica particles will be illustrated, but the present invention is not limited to this specific example.
シリカ粒子の表面修飾としては、特開２００５−１６２５３３号公報又は特開２０１０−２６９９８５号公報に記載された方法を適用することができる。例えば、シリカ粒子とカルボキシ基含有シランカップリング剤（例えば、（３−トリエトキシシリル）プロピルコハク酸無水物）とを混合して、十分に攪拌することにより、前記シリカ粒子の表面に前記カルボキシ基含有シランカップリング剤を共有結合させることができる。更に加熱して加水分解することにより、カルボキシ基が共有結合を介して固定されたシリカ粒子を得ることができる。 As the surface modification of the silica particles, the methods described in JP-A-2005-162533 or JP-A-2010-269985 can be applied. For example, the silica particles and a carboxy group-containing silane coupling agent (for example, (3-triethoxysilyl) propylsuccinic anhydride) are mixed and sufficiently stirred to cause the carboxy group on the surface of the silica particles. The contained silane coupling agent can be covalently bonded. By further heating and hydrolyzing, silica particles in which the carboxy group is fixed via a covalent bond can be obtained.
（Ａ）成分の平均粒子径の下限値は、好ましくは１５ｎｍであり、より好ましくは３０ｎｍである。（Ａ）成分の平均粒子径の上限値は、好ましくは１００ｎｍであり、より好ましくは７０ｎｍである。（Ａ）成分の平均粒子径が前記範囲であると、タングステンやコバルト等の導電体金属を含む半導体基板を、研磨欠陥の発生を抑制しつつ実用的な研磨速度で研磨できる場合がある。（Ａ）成分の平均粒子径は、製造された化学機械研磨用組成物を動的光散乱法による粒子径測定装置で測定することによって得られる。動的光散乱法による粒子径測定装置としては、ベックマン・コールター社製のナノ粒子アナライザー「ＤｅｌｓａＮａｎｏ Ｓ」、Ｍａｌｖｅｒｎ社製の「Ｚｅｔａｓｉｚｅｒ ｎａｎｏ ｚｓ」等が挙げられる。なお、動的光散乱法を用いて測定した平均粒子径は、一次粒子が複数個凝集して形成された二次粒子の平均粒子径を表している。 The lower limit of the average particle size of the component (A) is preferably 15 nm, more preferably 30 nm. The upper limit of the average particle size of the component (A) is preferably 100 nm, more preferably 70 nm. When the average particle size of the component (A) is within the above range, a semiconductor substrate containing a conductor metal such as tungsten or cobalt may be able to be polished at a practical polishing rate while suppressing the occurrence of polishing defects. The average particle size of the component (A) is obtained by measuring the produced composition for chemical mechanical polishing with a particle size measuring device by a dynamic light scattering method. Examples of the particle size measuring device by the dynamic light scattering method include a nanoparticle analyzer "DelsaNano S" manufactured by Beckman Coulter and "Zetasizer nano zs" manufactured by Malvern. The average particle size measured by the dynamic light scattering method represents the average particle size of the secondary particles formed by aggregating a plurality of primary particles.
（Ａ）成分のゼータ電位は、化学機械研磨用組成物のｐＨが１以上６以下の場合、化学機械研磨用組成物中において負電位であり、その負電位は−１０ｍＶ以下であることが好ましい。−１０ｍＶ以下の負電位であると、粒子間の静電反発力によって効果的に粒子同士の凝集を防ぐとともに、化学機械研磨の際に正電荷を帯びる基板を選択的に研磨できる場合がある。なお、ゼータ電位測定装置としては、大塚電子株式会社製の「ＥＬＳＺ−１」、Ｍａｌｖｅｒｎ社製の「Ｚｅｔａｓｉｚｅｒ ｎａｎｏ ｚｓ」等が挙げられる。（Ａ）成分のゼータ電位は、前述したカルボキシ基含有シランカップリング剤の添加量を増減することにより適宜調整することができる。 The zeta potential of the component (A) is a negative potential in the composition for chemical mechanical polishing when the pH of the composition for chemical mechanical polishing is 1 or more and 6 or less, and the negative potential is preferably -10 mV or less. .. When the negative potential is -10 mV or less, the electrostatic repulsive force between the particles effectively prevents the particles from agglutinating with each other, and in some cases, the substrate carrying a positive charge can be selectively polished during chemical mechanical polishing. Examples of the zeta potential measuring device include "ELSZ-1" manufactured by Otsuka Electronics Co., Ltd., "Zetasizer nano zs" manufactured by Malvern, and the like. The zeta potential of the component (A) can be appropriately adjusted by increasing or decreasing the amount of the above-mentioned carboxy group-containing silane coupling agent added.
（Ａ）成分の含有量の下限値は、化学機械研磨用組成物の全質量を１００質量％としたときに、好ましくは０．１質量％であり、より好ましくは０．５質量％であり、特に好ましくは１質量％である。（Ａ）成分の含有量の上限値は、化学機械研磨用組成物の全質量を１００質量％としたときに、好ましくは１０質量％であり、より好ましくは８質量％であり、特に好ましくは５質量％である。（Ａ）成分の含有量が前記範囲であると、タングステンやコバルト等の導電体金属を含む半導体基板を、研磨欠陥の発生を抑制しつつ実用的な研磨速度で研磨できる場合がある。 The lower limit of the content of the component (A) is preferably 0.1% by mass, more preferably 0.5% by mass, when the total mass of the chemical mechanical polishing composition is 100% by mass. , Particularly preferably 1% by mass. The upper limit of the content of the component (A) is preferably 10% by mass, more preferably 8% by mass, and particularly preferably 8% by mass when the total mass of the chemical mechanical polishing composition is 100% by mass. It is 5% by mass. When the content of the component (A) is within the above range, a semiconductor substrate containing a conductor metal such as tungsten or cobalt may be able to be polished at a practical polishing rate while suppressing the occurrence of polishing defects.
１．２．（Ｂ）成分
本実施形態に係る化学機械研磨用組成物は、（Ｂ）水酸基及びエーテル基を有する化合物を含有する。（Ｂ）成分を含有することにより、研磨工程における蒸発による化学機械研磨用組成物の特性変化を抑制でき、安定した研磨特性を発現することができる。これにより、タングステンやコバルト等の導電体金属を含む半導体基板を、研磨欠陥の発生を抑制しつつ実用的な研磨速度で研磨することができる。1.2. (B) Component The chemical mechanical polishing composition according to the present embodiment contains (B) a compound having a hydroxyl group and an ether group. By containing the component (B), it is possible to suppress changes in the characteristics of the composition for chemical mechanical polishing due to evaporation in the polishing step, and it is possible to exhibit stable polishing characteristics. This makes it possible to polish a semiconductor substrate containing a conductive metal such as tungsten or cobalt at a practical polishing rate while suppressing the occurrence of polishing defects.
（Ｂ）成分は、分子内に１以上の水酸基及び１以上のエーテル基を有する化合物であれば特に限定されないが、研磨工程において上昇する被研磨面の温度よりも高い標準沸点を有することが好ましい。（Ｂ）成分の標準沸点は、好ましくは８０℃以上であり、より好ましくは１００℃以上である。（Ｂ）成分の標準沸点が前記範囲であると、研磨工程における蒸発による化学機械研磨用組成物の特性変化を抑制しやすくすることができる。なお、標準沸点とは、１気圧のときの沸点のことをいう。 The component (B) is not particularly limited as long as it is a compound having 1 or more hydroxyl groups and 1 or more ether groups in the molecule, but it is preferable that the component (B) has a standard boiling point higher than the temperature of the surface to be polished that rises in the polishing step. .. The standard boiling point of the component (B) is preferably 80 ° C. or higher, more preferably 100 ° C. or higher. When the standard boiling point of the component (B) is in the above range, it is possible to easily suppress changes in the characteristics of the chemical mechanical polishing composition due to evaporation in the polishing step. The standard boiling point is the boiling point at 1 atm.
このような（Ｂ）成分としては、グリコールエーテルが好ましい。グリコールエーテルの具体例としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノアリルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、３−メトキシ−３−メチル−１−ブタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノベンジルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノプロピルエーテル、トリエチレングリコールモノブチルエーテル、トリプロピレングリコールモノブチルエーテル等を挙げることができる。これらの（Ｂ）成分は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 As such a component (B), glycol ether is preferable. Specific examples of the glycol ether include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoallyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene. Glycol Monopropyl Ether, Propylene Glycol Monobutyl Ether, 3-methoxy-3-methyl-1-butanol, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monopropyl Ether, Diethylene Glycol Monobutyl Ether, Diethylene Glycol Monobenzyl Ether, Dipropylene Glycol Monomethyl Ether , Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monobutyl Ether, Triethylene Glycol Monomethyl Ether, Triethylene Glycol Monoethyl Ether, Triethylene Glycol Monopropyl Ether, Triethylene Glycol Monobutyl Ether, Tripropylene Glycol Examples thereof include monobutyl ether. These components (B) may be used alone or in combination of two or more.
（Ｂ）成分の含有量の下限値は、化学機械研磨用組成物の全質量を１００質量％としたときに、好ましくは０．０００１質量％であり、より好ましくは０．０００５質量％であり、特に好ましくは０．００１質量％である。（Ｂ）成分の含有量の上限値は、化学機械研磨用組成物の全質量を１００質量％としたときに、好ましくは０．０５質量％であり、より好ましくは０．０４質量％であり、特に好ましくは０．０２質量％である。（Ｂ）成分の含有量が前記範囲であると、研磨工程における蒸発による化学機械研磨用組成物の特性変化を抑制しやすく、安定した研磨特性を発現させやすい。 The lower limit of the content of the component (B) is preferably 0.0001% by mass, more preferably 0.0005% by mass, when the total mass of the chemical mechanical polishing composition is 100% by mass. , Particularly preferably 0.001% by mass. The upper limit of the content of the component (B) is preferably 0.05% by mass, more preferably 0.04% by mass, when the total mass of the chemical mechanical polishing composition is 100% by mass. , Particularly preferably 0.02% by mass. When the content of the component (B) is within the above range, it is easy to suppress the change in the characteristics of the chemical mechanical polishing composition due to evaporation in the polishing step, and it is easy to develop stable polishing characteristics.
１．３．液状媒体
本実施形態に係る化学機械研磨用組成物は、液状媒体を含有する。液状媒体としては、水、水及びアルコールの混合媒体、水及び水との相溶性を有する有機溶媒を含む混合媒体等が挙げられる。これらの中でも、水、水及びアルコールの混合媒体を用いることが好ましく、水を用いることがより好ましい。水としては、特に制限されるものではないが、純水が好ましい。水は、化学機械研磨用組成物の構成材料の残部として配合されていればよく、水の含有量については特に制限はない。1.3. Liquid medium The composition for chemical mechanical polishing according to this embodiment contains a liquid medium. Examples of the liquid medium include a mixed medium of water, water and alcohol, a mixed medium containing an organic solvent compatible with water and water, and the like. Among these, it is preferable to use a mixed medium of water, water and alcohol, and it is more preferable to use water. The water is not particularly limited, but pure water is preferable. Water may be blended as the remainder of the constituent material of the chemical mechanical polishing composition, and the content of water is not particularly limited.
１．４．その他の添加剤
本実施形態に係る化学機械研磨用組成物は、必要に応じて、酸化剤、有機酸、界面活性剤、水溶性高分子、防蝕剤、ｐＨ調整剤等の添加剤をさらに含有してもよい。以下、各添加剤について説明する。1.4. Other Additives The chemical mechanical polishing composition according to the present embodiment further contains additives such as an oxidizing agent, an organic acid, a surfactant, a water-soluble polymer, an anticorrosive agent, and a pH adjuster, if necessary. You may. Hereinafter, each additive will be described.
＜酸化剤＞
本実施形態に係る化学機械研磨用組成物は、酸化剤を含有してもよい。酸化剤を含有することにより、タングステンやコバルト等の金属を酸化して研磨液成分との錯化反応を促すことにより、被研磨面に脆弱な改質層を作り出すことができるため、研磨速度が向上する場合がある。<Oxidizing agent>
The composition for chemical mechanical polishing according to this embodiment may contain an oxidizing agent. By containing an oxidizing agent, a metal such as tungsten or cobalt is oxidized to promote a complex reaction with the polishing liquid component, so that a fragile modified layer can be created on the surface to be polished, so that the polishing speed is increased. May improve.
酸化剤としては、例えば、過硫酸アンモニウム、過硫酸カリウム、過酸化水素、硝酸第二鉄、硝酸二アンモニウムセリウム、次亜塩素酸カリウム、オゾン、過ヨウ素酸カリウム、過酢酸等が挙げられる。これらの酸化剤のうち、酸化力及び取り扱いやすさを考慮すると、過硫酸アンモニウム、過硫酸カリウム、過酸化水素が好ましく、過酸化水素がより好ましい。これらの酸化剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the oxidizing agent include ammonium persulfate, potassium persulfate, hydrogen peroxide, ferric nitrate, diammonium cerium nitrate, potassium hypochlorite, ozone, potassium periodate, peracetic acid and the like. Among these oxidizing agents, ammonium persulfate, potassium persulfate, and hydrogen peroxide are preferable, and hydrogen peroxide is more preferable, in consideration of oxidizing power and ease of handling. These oxidizing agents may be used alone or in combination of two or more.
本実施形態に係る化学機械研磨用組成物が酸化剤を含有する場合において、酸化剤の含有量は、化学機械研磨用組成物の全質量を１００質量％としたときに、好ましくは０．１〜５質量％であり、より好ましくは０．３〜４質量％であり、特に好ましくは０．５〜３質量％である。なお、酸化剤は、化学機械研磨用組成物中で分解されやすいため、ＣＭＰの研磨工程を行う直前に添加されることが望ましい。 When the composition for chemical mechanical polishing according to the present embodiment contains an oxidizing agent, the content of the oxidizing agent is preferably 0.1 when the total mass of the composition for chemical mechanical polishing is 100% by mass. It is ~ 5% by mass, more preferably 0.3 to 4% by mass, and particularly preferably 0.5 to 3% by mass. Since the oxidizing agent is easily decomposed in the chemical mechanical polishing composition, it is desirable that the oxidizing agent is added immediately before the CMP polishing step.
＜有機酸＞
本実施形態に係る化学機械研磨用組成物は、有機酸を含有してもよい。有機酸を含有することにより、有機酸が被研磨面に配位して研磨速度が向上するとともに、研磨中における金属塩の析出を抑制できる場合がある。また、有機酸が被研磨面に配位することで、被研磨面のエッチング及び腐食によるダメージを低減できる場合がある。<Organic acid>
The composition for chemical mechanical polishing according to this embodiment may contain an organic acid. By containing the organic acid, the organic acid may be coordinated to the surface to be polished to improve the polishing rate and suppress the precipitation of metal salts during polishing. Further, by coordinating the organic acid to the surface to be polished, damage due to etching and corrosion of the surface to be polished may be reduced.
このような有機酸としては、特に制限されないが、例えば、マロン酸、クエン酸、リンゴ酸、酒石酸、シュウ酸、乳酸、イミノジ酢酸等の飽和カルボン酸；アクリル酸、メタクリル酸、クロトン酸、２−ブテン酸、２−メチル−３−ブテン酸、２−ヘキセン酸、３−メチル−２−ヘキセン酸等の不飽和モノカルボン酸；マレイン酸、フマル酸、シトラコン酸、メサコン酸、２−ペンテン二酸、イタコン酸、アリルマロン酸、イソプロピリデンコハク酸、２，４−ヘキサジエン二酸、アセチレンジカルボン酸等の不飽和ジカルボン酸；トリメリット酸等の芳香族カルボン酸；グリシン、アラニン、アスパラギン酸、グルタミン酸、リシン、アルギニン、トリプトファン、ヒスチジン、芳香族アミノ酸、複素環型アミノ酸等のアミノ酸、及びこれらの塩が挙げられる。これらの有機酸は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Such organic acids are not particularly limited, but are, for example, saturated carboxylic acids such as malonic acid, citric acid, malic acid, tartaric acid, oxalic acid, lactic acid, and iminodiacetic acid; acrylic acid, methacrylic acid, crotonic acid, 2-. Unsaturated monocarboxylic acids such as butenoic acid, 2-methyl-3-butenoic acid, 2-hexenoic acid, 3-methyl-2-hexenoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-pentenodiic acid , Itaconic acid, allylmaronic acid, isopropyridene succinic acid, 2,4-hexadienodic acid, unsaturated dicarboxylic acid such as acetylenedicarboxylic acid; aromatic carboxylic acid such as trimellitic acid; glycine, alanine, aspartic acid, glutamate, lysine , Arginine, tryptophan, histidine, aromatic amino acids, heterocyclic amino acids and other amino acids, and salts thereof. These organic acids may be used alone or in combination of two or more.
本実施形態に係る化学機械研磨用組成物が有機酸を含有する場合において、有機酸の含有量は、化学機械研磨用組成物の全質量を１００質量％としたときに、好ましくは０．０１〜５質量％であり、より好ましくは０．０３〜１質量％であり、特に好ましくは０．１〜０．５質量％である。 When the composition for chemical mechanical polishing according to the present embodiment contains an organic acid, the content of the organic acid is preferably 0.01 when the total mass of the composition for chemical mechanical polishing is 100% by mass. It is ~ 5% by mass, more preferably 0.03 to 1% by mass, and particularly preferably 0.1 to 0.5% by mass.
＜界面活性剤＞
本実施形態に係る化学機械研磨用組成物は、界面活性剤を含有してもよい。界面活性剤を含有することにより、化学機械研磨用組成物に適度な粘性を付与できる場合がある。化学機械研磨用組成物の粘度は、２５℃において０．５ｍＰａ・ｓ以上１０ｍＰａ・ｓ未満となるように調整することが好ましい。<Surfactant>
The chemical mechanical polishing composition according to this embodiment may contain a surfactant. By containing a surfactant, it may be possible to impart an appropriate viscosity to the composition for chemical mechanical polishing. The viscosity of the chemical mechanical polishing composition is preferably adjusted to be 0.5 mPa · s or more and less than 10 mPa · s at 25 ° C.
界面活性剤としては、特に制限されず、アニオン性界面活性剤、カチオン性界面活性剤、非イオン性界面活性剤等が挙げられる。 The surfactant is not particularly limited, and examples thereof include anionic surfactants, cationic surfactants, and nonionic surfactants.
アニオン性界面活性剤としては、例えば、脂肪酸石鹸、アルキルエーテルカルボン酸塩等のカルボン酸塩；アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、α−オレフィンスルホン酸塩等のスルホン酸塩；高級アルコール硫酸エステル塩、アルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩等の硫酸塩；パーフルオロアルキル化合物等の含フッ素系界面活性剤等が挙げられる。カチオン性界面活性剤としては、例えば、脂肪族アミン塩、脂肪族アンモニウム塩等が挙げられる。非イオン性界面活性剤としては、例えば、アセチレングリコール、アセチレングリコールエチレンオキサイド付加物、アセチレンアルコール等の三重結合を有する非イオン性界面活性剤；ポリエチレングリコール型界面活性剤等が挙げられる。これらの界面活性剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the anionic surfactant include carboxylates such as fatty acid soaps and alkyl ether sulfonates; sulfonates such as alkylbenzene sulfonates, alkylnaphthalene sulfonates and α-olefin sulfonates; higher alcohol sulfates. Sulfates such as ester salts, alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates; fluorine-containing surfactants such as perfluoroalkyl compounds can be mentioned. Examples of the cationic surfactant include aliphatic amine salts and aliphatic ammonium salts. Examples of the nonionic surfactant include a nonionic surfactant having a triple bond such as acetylene glycol, an acetylene glycol ethylene oxide adduct, and an acetylene alcohol; a polyethylene glycol type surfactant and the like. These surfactants may be used alone or in combination of two or more.
本実施形態に係る化学機械研磨用組成物が界面活性剤を含有する場合において、界面活性剤の含有量は、化学機械研磨用組成物の全質量を１００質量％としたときに、好ましくは０．００１〜５質量％であり、より好ましくは０．００１〜３質量％であり、特に好ましくは０．０１〜１質量％である。 When the composition for chemical mechanical polishing according to the present embodiment contains a surfactant, the content of the surfactant is preferably 0 when the total mass of the composition for chemical mechanical polishing is 100% by mass. It is .001 to 5% by mass, more preferably 0.001 to 3% by mass, and particularly preferably 0.01 to 1% by mass.
＜水溶性高分子＞
本実施形態に係る化学機械研磨用組成物は、水溶性高分子を含有してもよい。水溶性高分子には、被研磨面の表面に吸着して研磨摩擦を低減させる効果がある。この効果により、被研磨面における研磨欠陥の発生を低減できる場合がある。<Water-soluble polymer>
The composition for chemical mechanical polishing according to this embodiment may contain a water-soluble polymer. The water-soluble polymer has the effect of adsorbing to the surface of the surface to be polished and reducing polishing friction. Due to this effect, the occurrence of polishing defects on the surface to be polished may be reduced.
水溶性高分子としては、ポリ（メタ）アクリルアミド、ポリ（メタ）アクリル酸、ポリビニルアルコール、ポリビニルピロリドン、ヒドロキシエチルセルロース、カルボキシメチルセルロース、（メタ）アクリル酸とマレイン酸の共重合体等が挙げられる。 Examples of the water-soluble polymer include poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, and a copolymer of (meth) acrylic acid and maleic acid.
水溶性高分子の重量平均分子量（Ｍｗ）は、好ましくは１，０００〜１，０００，０００であり、より好ましくは３，０００〜８００，０００である。水溶性高分子の重量平均分子量が前記範囲にあると、配線材料等の被研磨面に吸着しやすくなり、研磨摩擦をより低減できる場合がある。その結果、被研磨面における研磨欠陥の発生をより効果的に低減できる場合がある。なお、本明細書中における「重量平均分子量（Ｍｗ）」とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によって測定されたポリエチレングリコール換算の重量平均分子量のことを指す。 The weight average molecular weight (Mw) of the water-soluble polymer is preferably 1,000 to 1,000,000, more preferably 3,000 to 800,000. When the weight average molecular weight of the water-soluble polymer is within the above range, it is likely to be adsorbed on the surface to be polished such as a wiring material, and polishing friction may be further reduced. As a result, the occurrence of polishing defects on the surface to be polished may be reduced more effectively. The "weight average molecular weight (Mw)" in the present specification refers to a polyethylene glycol-equivalent weight average molecular weight measured by GPC (gel permeation chromatography).
本実施形態に係る化学機械研磨用組成物が水溶性高分子を含有する場合において、水溶性高分子の含有量は、化学機械研磨用組成物の全質量を１００質量％としたときに、好ましくは０．０１〜１質量％であり、より好ましくは０．０３〜０．５質量％である。 When the composition for chemical mechanical polishing according to the present embodiment contains a water-soluble polymer, the content of the water-soluble polymer is preferably 100% by mass when the total mass of the composition for chemical mechanical polishing is 100% by mass. Is 0.01 to 1% by mass, more preferably 0.03 to 0.5% by mass.
なお、水溶性高分子の含有量は、水溶性高分子の重量平均分子量（Ｍｗ）にも依存するが、化学機械研磨用組成物の２５℃における粘度が０．５ｍＰａ・ｓ以上１０ｍＰａ・ｓ未満となるように調整することが好ましい。化学機械研磨用組成物の２５℃における粘度が０．５ｍＰａ・ｓ以上１０ｍＰａ・ｓ未満であると、配線材料等を高速で研磨しやすく、粘度が適正であるため研磨布上に安定して化学機械研磨用組成物を供給することができる。 The content of the water-soluble polymer depends on the weight average molecular weight (Mw) of the water-soluble polymer, but the viscosity of the chemical mechanical polishing composition at 25 ° C. is 0.5 mPa · s or more and less than 10 mPa · s. It is preferable to adjust so as to be. When the viscosity of the chemical mechanical polishing composition at 25 ° C. is 0.5 mPa · s or more and less than 10 mPa · s, it is easy to polish the wiring material at high speed, and the viscosity is appropriate, so that the chemical is stably applied on the polishing cloth. A composition for mechanical polishing can be supplied.
＜防蝕剤＞
本実施形態に係る化学機械研磨用組成物は、防蝕剤を含有してもよい。防蝕剤としては、例えば、ベンゾトリアゾール及びその誘導体が挙げられる。ここで、ベンゾトリアゾール誘導体とは、ベンゾトリアゾールの有する１個又は２個以上の水素原子を、例えば、カルボキシ基、メチル基、アミノ基、ヒドロキシ基等で置換したものをいう。ベンゾトリアゾール誘導体の具体例としては、４−カルボキシルベンゾトリアゾール、７−カルボキシベンゾトリアゾール、ベンゾトリアゾールブチルエステル、１−ヒドロキシメチルベンゾトリアゾール、１−ヒドロキシベンゾトリアゾール、及びこれらの塩等が挙げられる。<Corrosion proofing agent>
The composition for chemical mechanical polishing according to the present embodiment may contain an anticorrosive agent. Examples of the anticorrosive agent include benzotriazole and its derivatives. Here, the benzotriazole derivative refers to one in which one or more hydrogen atoms of benzotriazole are substituted with, for example, a carboxy group, a methyl group, an amino group, a hydroxy group or the like. Specific examples of the benzotriazole derivative include 4-carboxybenzotriazole, 7-carboxybenzotriazole, benzotriazole butyl ester, 1-hydroxymethylbenzotriazole, 1-hydroxybenzotriazole, and salts thereof.
本実施形態に係る化学機械研磨用組成物が防蝕剤を含有する場合において、防蝕剤の含有量は、化学機械研磨用組成物の全質量を１００質量％としたときに、好ましくは１質量％以下であり、より好ましくは０．００１〜０．１質量％である。 When the composition for chemical mechanical polishing according to the present embodiment contains an anticorrosive agent, the content of the anticorrosive agent is preferably 1% by mass when the total mass of the composition for chemical mechanical polishing is 100% by mass. It is more preferably 0.001 to 0.1% by mass.
＜ｐＨ調整剤＞
本実施形態に係る化学機械研磨用組成物は、さらに必要に応じてｐＨ調整剤を含有してもよい。ｐＨ調整剤としては、水酸化カリウム、エチレンジアミン、モノエタノールアミン、ＴＭＡＨ（テトラメチルアンモニウムヒドロキシド）、ＴＥＡＨ（テトラエチルアンモニウムヒドロキシド）、アンモニア等の塩基；リン酸、硫酸、塩酸、硝酸等の無機酸、及びこれらの塩が挙げられ、これらの１種以上を用いることができる。<pH adjuster>
The chemical mechanical polishing composition according to the present embodiment may further contain a pH adjuster, if necessary. Examples of the pH adjuster include bases such as potassium hydroxide, ethylenediamine, monoethanolamine, TMAH (tetramethylammonium hydroxide), TEAH (tetraethylammonium hydroxide) and ammonia; and inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid and nitric acid. , And salts thereof, and one or more of these can be used.
１．５．ｐＨ
本実施形態に係る化学機械研磨用組成物のｐＨは、特に制限されないが、好ましくは２以上５以下であり、より好ましくは２以上４以下である。ｐＨが前記範囲にあると、化学機械研磨用組成物中の（Ａ）成分の分散性が向上することで、化学機械研磨用組成物の貯蔵安定性が良好となるため好ましい。1.5. pH
The pH of the chemical mechanical polishing composition according to the present embodiment is not particularly limited, but is preferably 2 or more and 5 or less, and more preferably 2 or more and 4 or less. When the pH is in the above range, the dispersibility of the component (A) in the composition for chemical mechanical polishing is improved, and the storage stability of the composition for chemical mechanical polishing is improved, which is preferable.
なお、本実施形態に係る化学機械研磨用組成物のｐＨは、例えば、有機酸やｐＨ調整剤等の含有量を適宜増減することにより調整することができる。 The pH of the chemical mechanical polishing composition according to this embodiment can be adjusted, for example, by appropriately increasing or decreasing the content of an organic acid, a pH adjuster, or the like.
本発明において、ｐＨとは、水素イオン指数のことを指し、その値は、２５℃、１気圧の条件下で市販のｐＨメーター（例えば、株式会社堀場製作所製、卓上型ｐＨメーター）を用いて、測定することができる。 In the present invention, the pH refers to a hydrogen ion index, and the value thereof is a commercially available pH meter (for example, a tabletop pH meter manufactured by HORIBA, Ltd.) under the condition of 25 ° C. and 1 atm. , Can be measured.
１．６．用途
本実施形態に係る化学機械研磨用組成物は、半導体装置を構成する複数種の材料を有する半導体基板を化学機械研磨するための研磨材料として好適である。例えば、前記半導体基板は、タングステンやコバルト等の導電体金属の他、シリコン酸化膜、シリコン窒化膜、アモルファスシリコン等の絶縁膜材料や、チタン、窒化チタン、窒化タンタル等のバリアメタル材料を有していてもよい。1.6. Applications The chemical mechanical polishing composition according to this embodiment is suitable as a polishing material for chemical mechanical polishing of a semiconductor substrate having a plurality of types of materials constituting a semiconductor device. For example, the semiconductor substrate has a conductive metal such as tungsten and cobalt, an insulating film material such as a silicon oxide film, a silicon nitride film, and amorphous silicon, and a barrier metal material such as titanium, titanium nitride, and tantalum nitride. May be.
本実施形態に係る化学機械研磨用組成物の特に好適な研磨対象は、タングステンを含む配線層が設けられた半導体基板等の被処理体である。具体的には、ヴィアホールを有するシリコン酸化膜と、前記シリコン酸化膜上にバリアメタル膜を介して設けられたタングステン膜と、を含む被処理体が挙げられる。本実施形態に係る化学機械研磨用組成物を用いることによって、タングステン膜を高速かつ平坦に研磨できるだけでなく、タングステン膜とシリコン酸化膜等の絶縁膜とが共存する被研磨面に対しても研磨欠陥の発生を抑制しながら高速かつ平坦に研磨することができる。 A particularly suitable polishing target for the chemical mechanical polishing composition according to the present embodiment is a workpiece such as a semiconductor substrate provided with a wiring layer containing tungsten. Specific examples thereof include a silicon oxide film having a via hole and a tungsten film provided on the silicon oxide film via a barrier metal film. By using the chemical mechanical polishing composition according to the present embodiment, not only the tungsten film can be polished at high speed and flatly, but also the surface to be polished in which the tungsten film and the insulating film such as the silicon oxide film coexist can be polished. It is possible to polish at high speed and flatly while suppressing the occurrence of defects.
１．７．化学機械研磨用組成物の調製方法
本実施形態に係る化学機械研磨用組成物は、水等の液状媒体に上述の各成分を溶解又は分散させることにより調製することができる。溶解又は分散させる方法は、特に制限されず、均一に溶解又は分散できればどのような方法を適用してもよい。また、上述の各成分の混合順序や混合方法についても特に制限されない。1.7. Method for Preparing Composition for Chemical Mechanical Polishing The composition for chemical mechanical polishing according to this embodiment can be prepared by dissolving or dispersing each of the above-mentioned components in a liquid medium such as water. The method for dissolving or dispersing is not particularly limited, and any method may be applied as long as it can be uniformly dissolved or dispersed. Further, the mixing order and mixing method of each of the above-mentioned components are not particularly limited.
また、本実施形態に係る化学機械研磨用組成物は、濃縮タイプの原液として調製し、使用時に水等の液状媒体で希釈して使用することもできる。 Further, the composition for chemical mechanical polishing according to the present embodiment can be prepared as a concentrated type stock solution and diluted with a liquid medium such as water at the time of use.
２．化学機械研磨方法
本発明の一実施形態に係る研磨方法は、上述した化学機械研磨用組成物を用いて、半導体基板を研磨する工程を含む。以下、本実施形態に係る化学機械研磨方法の一具体例について、図面を用いながら詳細に説明する。2. 2. Chemical Mechanical Polishing Method The polishing method according to an embodiment of the present invention includes a step of polishing a semiconductor substrate by using the above-mentioned chemical mechanical polishing composition. Hereinafter, a specific example of the chemical mechanical polishing method according to the present embodiment will be described in detail with reference to the drawings.
２．１．被処理体
図１は、本実施形態に係る化学機械研磨方法の使用に適した被処理体を模式的に示した断面図である。被処理体１００は、以下の工程（１）〜工程（４）を経ることにより形成される。2.1. FIG. 1 is a cross-sectional view schematically showing an object to be treated suitable for use in the chemical mechanical polishing method according to the present embodiment. The object to be treated 100 is formed by going through the following steps (1) to (4).
（１）まず、図１に示すように、基体１０を用意する。基体１０は、例えばシリコン基板とその上に形成されたシリコン酸化膜とから構成されていてもよい。さらに、基体１０には、（図示しない）トランジスタ等の機能デバイスが形成されていてもよい。次に、基体１０の上に、熱酸化法を用いて絶縁膜であるシリコン酸化膜１２を形成する。
(1) First, as shown in FIG. 1, the
（２）次いで、シリコン酸化膜１２をパターニングする。得られたパターンをマスクとして、フォトリソグラフィー法によりシリコン酸化膜１２にヴィアホール１４を形成する。
(2) Next, the
（３）次いで、スパッタ等を適用してシリコン酸化膜１２の表面及びヴィアホール１４の内壁面にバリアメタル膜１６を形成する。タングステンとシリコンとの電気的接触があまり良好でないため、バリアメタル膜を介在させることで良好な電気的接触を実現している。バリアメタル膜１６としては、チタン及び／又は窒化チタンが挙げられる。
(3) Next, a
（４）次いで、ＣＶＤ法を適用してタングステン膜１８を堆積させる。
(4) Next, the CVD method is applied to deposit the
以上の工程により、被処理体１００が形成される。 By the above steps, the object to be processed 100 is formed.
２．２．化学機械研磨方法
２．２．１．第１研磨工程
図２は、第１研磨工程終了時での被処理体を模式的に示した断面図である。第１研磨工程では、図２に示すように、上述の化学機械研磨用組成物を用いてバリアメタル膜１６が露出するまでタングステン膜１８を研磨する。2.2. Chemical mechanical polishing method 2.2.1. First Polishing Step FIG. 2 is a cross-sectional view schematically showing an object to be processed at the end of the first polishing step. In the first polishing step, as shown in FIG. 2, the
２．２．２．第２研磨工程
図３は、第２研磨工程終了時での被処理体を模式的に示した断面図である。第２研磨工程では、図３に示すように、上述の化学機械研磨用組成物を用いてシリコン酸化膜１２、バリアメタル膜１６及びタングステン膜１８を研磨する。第２研磨工程を経ることにより、被研磨面の平坦性に優れた次世代型の半導体装置２００を製造することができる。2.2.2. 2nd polishing process FIG. 3 is a cross-sectional view schematically showing an object to be processed at the end of the second polishing process. In the second polishing step, as shown in FIG. 3, the
なお、上記の通り、上述の化学機械研磨用組成物は、半導体装置を構成する複数種の材料を有する半導体基板を化学機械研磨するための研磨材料として好適である。そのため、本実施形態に係る化学機械研磨方法の第１研磨工程及び第２研磨工程において、同一組成の化学機械研磨用組成物を用いることができるので、生産ラインのスループットが向上する。 As described above, the above-mentioned composition for chemical mechanical polishing is suitable as a polishing material for chemically polishing a semiconductor substrate having a plurality of types of materials constituting a semiconductor device. Therefore, in the first polishing step and the second polishing step of the chemical mechanical polishing method according to the present embodiment, the composition for chemical mechanical polishing having the same composition can be used, so that the throughput of the production line is improved.
２．３．化学機械研磨装置
上述の第１研磨工程及び第２研磨工程には、例えば図４に示すような研磨装置３００を用いることができる。図４は、研磨装置３００を模式的に示した斜視図である。上述の第１研磨工程及び第２研磨工程は、スラリー供給ノズル４２からスラリー（化学機械研磨用組成物）４４を供給し、かつ研磨布４６が貼付されたターンテーブル４８を回転させながら、半導体基板５０を保持したキャリアーヘッド５２を当接させることにより行う。なお、図４には、水供給ノズル５４及びドレッサー５６も併せて示してある。2.3. Chemical mechanical polishing apparatus For the first polishing step and the second polishing step described above, for example, the polishing
キャリアーヘッド５２の研磨荷重は、１０〜９８０ｈＰａの範囲内で選択することができ、好ましくは３０〜４９０ｈＰａである。また、ターンテーブル４８及びキャリアーヘッド５２の回転数は１０〜４００ｒｐｍの範囲内で適宜選択することができ、好ましくは３０〜１５０ｒｐｍである。スラリー供給ノズル４２から供給されるスラリー（化学機械研磨用組成物）４４の流量は、１０〜１，０００ｍＬ／分の範囲内で選択することができ、好ましくは５０〜４００ｍＬ／分である。
The polishing load of the
市販の研磨装置としては、例えば、荏原製作所社製、型式「ＥＰＯ−１１２」、「ＥＰＯ−２２２」；ラップマスターＳＦＴ社製、型式「ＬＧＰ−５１０」、「ＬＧＰ−５５２」；アプライドマテリアル社製、型式「Ｍｉｒｒａ」、「Ｒｅｆｌｅｘｉｏｎ」；Ｇ＆Ｐ ＴＥＣＨＮＯＬＯＧＹ社製、型式「ＰＯＬＩ−４００Ｌ」；ＡＭＡＴ社製、型式「Ｒｅｆｌｅｘｉｏｎ ＬＫ」等が挙げられる。 Examples of commercially available polishing equipment include, for example, Ebara Corporation, model "EPO-112", "EPO-222"; Lapmaster SFT, model "LGP-510", "LGP-552"; Applied Materials. , Model "Mirra", "Reflexion"; manufactured by G & P TECHNOLOGY, model "POLI-400L"; manufactured by AMAT, model "Reflexion LK" and the like.
３．実施例
以下、本発明を実施例により説明するが、本発明はこれらの実施例により何ら限定されるものではない。なお、本実施例における「部」及び「％」は、特に断らない限り質量基準である。3. 3. Examples The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" and "%" in this Example are based on mass unless otherwise specified.
３．１．シリカ粒子水分散体の調製
３．１．１．水分散体Ａの調製
容量２０００ｃｍ３のフラスコに、ＰＬ−３（扶桑化学工業株式会社製、１９．５％コロイダルシリカ）を２０００ｇ入れ、６０℃になるまで加熱した。その後、（３−トリエトキシシリル）プロピルコハク酸無水物（東京化成工業株式会社製）６．０ｇを加え、６０℃で加熱、４時間反応を続けた。冷却後、カルボン酸修飾シリカ粒子の水分散体Ａを得た。3.1. Preparation of water dispersion of silica particles 3.1.1. Preparation of Aqueous Dispersion A 2000 g of PL-3 (19.5% colloidal silica manufactured by Fuso Chemical Industry Co., Ltd.) was placed in a flask having a capacity of 2000 cm 3 and heated to 60 ° C. Then, 6.0 g of (3-triethoxysilyl) propyl succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was heated at 60 ° C. and the reaction was continued for 4 hours. After cooling, an aqueous dispersion A of carboxylic acid-modified silica particles was obtained.
３．１．２．水分散体Ｂの調製
純水７８７．９ｇ、２５％アンモニア水（富士フイルム和光純薬株式会社製）７８６．０ｇ、メタノール（富士フイルム和光純薬株式会社製）１２９２４ｇの混合液に、テトラメトキシシラン（東京化成工業株式会社製）１５２２．２ｇとメタノール４１３．０ｇの混合液を、液温３５℃に保ちつつ５５分かけて滴下して、加水分解したシリカゾル分散液を得た。このゾルを常圧下にて、２９００ｍｌまで加熱濃縮を行った。この濃縮液をさらに、常圧下、加熱蒸留しつつ、容量を一定に保ちつつ純水を滴下し、塔頂温が１００℃に達し、且つｐＨが８以下になったのを確認した時点で純水の滴下を終了して、シリカゾルを得た。作成したシリカゾル５４０ｇに、メタノール１９．０ｇと３−アミノプロピルトリメトキシシラン１．０ｇの混合液を、液温を保ちつつ１０分かけて滴下した後、常圧下、２時間還流を行った。その後、容量を一定に保ちつつ純水を滴下し、塔頂温が１００℃に達した時点で純水の滴下を終了して、アミノ修飾シリカ粒子の水分散体を得た。得られた水分散体を１５０℃、２４時間の真空乾燥を行い、アミノ修飾シリカ粒子を得た。3.1.2. Preparation of aqueous dispersion B Tetramethoxysilane in a mixture of 787.9 g of pure water, 786.0 g of 25% ammonia water (manufactured by Fujifilm Wako Pure Chemical Industry Co., Ltd.), and 12924 g of methanol (manufactured by Fujifilm Wako Pure Chemical Industry Co., Ltd.). A mixed solution of 1522.2 g and 413.0 g of methanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 55 minutes while maintaining the solution temperature at 35 ° C. to obtain a hydrolyzed silica sol dispersion. This sol was heated and concentrated to 2900 ml under normal pressure. While further heating and distilling this concentrated solution under normal pressure, pure water was dropped while keeping the volume constant, and when it was confirmed that the column top temperature reached 100 ° C. and the pH became 8 or less, it was pure. The dropping of water was completed to obtain a silica sol. A mixed solution of 19.0 g of methanol and 1.0 g of 3-aminopropyltrimethoxysilane was added dropwise to 540 g of the prepared silica sol over 10 minutes while maintaining the liquid temperature, and then reflux was performed under normal pressure for 2 hours. Then, pure water was dropped while keeping the volume constant, and when the column top temperature reached 100 ° C., the dropping of pure water was completed to obtain an aqueous dispersion of amino-modified silica particles. The obtained aqueous dispersion was vacuum dried at 150 ° C. for 24 hours to obtain amino-modified silica particles.
得られたアミノ修飾シリカ粒子を７０℃、１２時間の乾燥を行った。マロン酸（東京化成工業株式会社製）１．４ｇを、あらかじめ窒素フローした三つ口フラスコに量り取り、２０．０ｍｌのＮ−メチル−２−ピロリドン（ＮＭＰ、富士フイルム和光純薬株式会社製）を加えて、マロン酸が完全に溶解するまで攪拌した。この反応溶液にアミノ修飾シリカ粒子２．０ｇを加えて１時間の攪拌を行い、続いて、（２，３−ジヒドロ−２−チオキソ−３−ベンゾオキサゾリル）ホスホン酸ジフェニル（東京化成工業株式会社製）を６．２ｇ、トリエチルアミン（富士フイルム和光純薬株式会社製）を１．４ｍｌ加えて、室温で２４時間攪拌した。この反応溶液を一晩静置し、粒子を沈殿させ上澄み溶液を捨てた後、ＮＭＰで粒子を数回洗浄し、カルボン酸修飾シリカ粒子を得た。回収した粒子は１００℃、１２時間の真空乾燥を行い、溶媒を除去した。純水を適量加えて２０％のカルボン酸修飾シリカ粒子の水分散体Ｂを得た。 The obtained amino-modified silica particles were dried at 70 ° C. for 12 hours. Weigh 1.4 g of malonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) into a three-necked flask with nitrogen flow in advance, and weigh 20.0 ml of N-methyl-2-pyrrolidone (NMP, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Was added and stirred until the malonic acid was completely dissolved. 2.0 g of amino-modified silica particles were added to this reaction solution, and the mixture was stirred for 1 hour, followed by diphenyl phosphonate (2,3-dihydro-2-thioxo-3-benzoxazolyl) (Tokyo Chemical Industry Co., Ltd.). 6.2 g of (manufactured by the company) and 1.4 ml of triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at room temperature for 24 hours. The reaction solution was allowed to stand overnight, the particles were precipitated and the supernatant solution was discarded, and then the particles were washed with NMP several times to obtain carboxylic acid-modified silica particles. The recovered particles were vacuum dried at 100 ° C. for 12 hours to remove the solvent. An appropriate amount of pure water was added to obtain an aqueous dispersion B of 20% carboxylic acid-modified silica particles.
３．１．３．水分散体Ｃの調製
上記「３．１．２．水分散体Ｂの調製」と同様の方法にてアミノ修飾シリカ粒子を得た。得られたアミノ修飾シリカ粒子を７０℃、１２時間の真空乾燥を行った。クエン酸（東京化成工業株式会社製）１．４ｇを、あらかじめ窒素フローした三つ口フラスコに量り取り、２０．０ｍｌのＮ−メチル−２−ピロリドン（ＮＭＰ）を加えて、クエン酸が完全に溶解するまで攪拌した。この反応溶液にアミノ修飾シリカ粒子２．０ｇを加えて１時間の攪拌を行い、続いて、（２，３−ジヒドロ−２−チオキソ−３−ベンゾオキサゾリル）ホスホン酸ジフェニルを５．７ｇ、トリエチルアミン）を１．３ｍｌ加えて、室温で２４時間攪拌した。この反応溶液を一晩静置し、粒子を沈殿させ上澄み溶液を捨てた後、ＮＭＰで粒子を数回洗浄し、カルボン酸修飾シリカ粒子を得た。回収した粒子は１００℃、１２時間の真空乾燥を行い、溶媒を除去した。純水を適量加え２０％のカルボン酸修飾シリカ粒子の水分散体Ｃ得た。3.1.3. Preparation of Aqueous Dispersion C Amino-modified silica particles were obtained by the same method as in "3.1.2. Preparation of Aqueous Dispersion B" above. The obtained amino-modified silica particles were vacuum dried at 70 ° C. for 12 hours. Weigh 1.4 g of citric acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) into a three-necked flask that has been previously flowed with nitrogen, and add 20.0 ml of N-methyl-2-pyrrolidone (NMP) to completely complete the citric acid. Stirred until dissolved. 2.0 g of amino-modified silica particles were added to this reaction solution, and the mixture was stirred for 1 hour, followed by 5.7 g of diphenyl phosphonate (2,3-dihydro-2-thioxo-3-benzoxazolyl). 1.3 ml of triethylamine) was added, and the mixture was stirred at room temperature for 24 hours. The reaction solution was allowed to stand overnight, the particles were precipitated and the supernatant solution was discarded, and then the particles were washed with NMP several times to obtain carboxylic acid-modified silica particles. The recovered particles were vacuum dried at 100 ° C. for 12 hours to remove the solvent. An appropriate amount of pure water was added to obtain an aqueous dispersion C of 20% carboxylic acid-modified silica particles.
３．１．４．水分散体Ｄの調製
容量２０００ｃｍ３のフラスコに、ＰＬ−３（扶桑化学工業株式会社製、１９．５％コロイダルシリカ）を２０００ｇ入れ、６０℃になるまで加熱した。続けてシランカップリング剤として（３−トリエトキシシリル）プロピルコハク酸無水物１２．０ｇを加え、６０℃で加熱、４時間反応を続けた。冷却後、カルボン酸修飾シリカ粒子の水分散体Ｄを得た。3.1.4. Preparation of Aqueous Dispersion D 2000 g of PL-3 (19.5% colloidal silica manufactured by Fuso Chemical Industry Co., Ltd.) was placed in a flask having a capacity of 2000 cm 3 and heated to 60 ° C. Subsequently, 12.0 g of (3-triethoxysilyl) propyl succinic acid anhydride was added as a silane coupling agent, and the mixture was heated at 60 ° C. and the reaction was continued for 4 hours. After cooling, an aqueous dispersion D of carboxylic acid-modified silica particles was obtained.
３．１．５．水分散体Ｅの調製
容量２０００ｃｍ３のフラスコに、ＰＬ−３（扶桑化学工業株式会社製、１９．５％コロイダルシリカ）を２０００ｇ入れ、６０℃になるまで加熱した。続けてシランカップリング剤として（３−トリエトキシシリル）プロピルコハク酸無水物１８．０ｇを加え、６０℃で加熱、４時間反応を続けた。冷却後、カルボン酸修飾シリカ粒子の水分散体Ｅを得た。3.1.5. Preparation of Aqueous Dispersion E 2000 g of PL-3 (19.5% colloidal silica manufactured by Fuso Chemical Industry Co., Ltd.) was placed in a flask having a capacity of 2000 cm 3 and heated to 60 ° C. Subsequently, 18.0 g of (3-triethoxysilyl) propyl succinic acid anhydride was added as a silane coupling agent, and the mixture was heated at 60 ° C. and the reaction was continued for 4 hours. After cooling, an aqueous dispersion E of carboxylic acid-modified silica particles was obtained.
３．１．６．水分散体Ｆの調製
容量２０００ｃｍ３のフラスコに、２５質量％濃度のアンモニア水７０ｇ、イオン交換水４０ｇ、エタノール１７５ｇ及びテトラエトキシシラン２１ｇを投入し、１８０ｒｐｍで撹拌しながら６０℃に昇温した。６０℃のまま１時間撹拌した後冷却し、コロイダルシリカ／アルコール分散体を得た。次いで、エバポレータにより、８０℃でこの分散体にイオン交換水を添加しながらアルコール分を除去する操作を数回繰り返すことにより分散体中のアルコールを除き、固形分濃度１５％のシリカ分散液を調製した。3.1.6. The flask was volume 2000 cm 3 of aqueous dispersion F, ammonia water 70g of 25% strength by weight, ion-exchanged water 40 g, ethanol 175g and tetraethoxysilane 21g were charged and heated with stirring to 60 ° C. at 180 rpm. The mixture was stirred at 60 ° C. for 1 hour and then cooled to obtain a colloidal silica / alcohol dispersion. Next, the operation of removing the alcohol content while adding ion-exchanged water to the dispersion at 80 ° C. was repeated several times using an evaporator to remove the alcohol in the dispersion and prepare a silica dispersion having a solid content concentration of 15%. bottom.
イオン交換水５０ｇに酢酸５ｇを投入し、撹拌しながらさらにメルカプト基含有シランカップリング剤（信越化学工業株式会社製、商品名「ＫＢＥ８０３」）５ｇを徐々に滴下した。３０分後、調製しておいたシリカ分散液を１０００ｇ添加し、さらに１時間撹拌を継続した。その後、３１％過酸化水素水を２００ｇ投入し、４８時間室温にて放置することにより、スルホ基を有するシリカ粒子を含む水分散体Ｆを得た。 5 g of acetic acid was added to 50 g of ion-exchanged water, and 5 g of a mercapto group-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBE803") was gradually added dropwise while stirring. After 30 minutes, 1000 g of the prepared silica dispersion was added, and stirring was continued for another 1 hour. Then, 200 g of 31% hydrogen peroxide solution was added and left at room temperature for 48 hours to obtain an aqueous dispersion F containing silica particles having a sulfo group.
３．１．７．水分散体Ｇの調製
純水７８７．９ｇ、２６％アンモニア水７８６．０ｇ、メタノール１２９２４ｇの混合液に、テトラメトキシシラン１５２２．２ｇとメタノール４１３．０ｇの混合液を、液温３５℃に保ちつつ５５分かけて滴下した。その後、常圧下にて、２９００ｍｌまで加熱濃縮を行った。この濃縮液をさらに、常圧下、加熱蒸留しつつ、容量を一定に保ちつつ純水を滴下し、塔頂温が１００℃に達し、且つｐＨが８以下になったのを確認した時点で純水の滴下を終了し、シリカ分散液を調製した。3.1.7. Preparation of aqueous dispersion G A mixed solution of 787.9 g of pure water, 786.0 g of 26% ammonia water, and 12924 g of methanol was mixed with 1522.2 g of tetramethoxysilane and 413.0 g of methanol while keeping the liquid temperature at 35 ° C. It was dropped over 55 minutes. Then, under normal pressure, heat concentration was performed up to 2900 ml. While further heating and distilling this concentrated solution under normal pressure, pure water was dropped while keeping the volume constant, and when it was confirmed that the column top temperature reached 100 ° C. and the pH became 8 or less, it was pure. The dropping of water was completed, and a silica dispersion was prepared.
調製したシリカ分散液５４０ｇに、メタノール１９．０ｇと３−アミノプロピルトリエトキシシラン１．０ｇの混合液を、液温を保ちつつ１０分かけて滴下した後、常圧下、２時間還流を行った。その後、容量を一定に保ちつつ純水を滴下し、塔頂温が１００℃に達した時点で純水の滴下を終了して、アミノ基を有するシリカ粒子を含む水分散体Ｇを得た。 A mixed solution of 19.0 g of methanol and 1.0 g of 3-aminopropyltriethoxysilane was added dropwise to 540 g of the prepared silica dispersion over 10 minutes while maintaining the liquid temperature, and then reflux was performed under normal pressure for 2 hours. .. Then, pure water was dropped while keeping the capacity constant, and when the column top temperature reached 100 ° C., the dropping of pure water was terminated to obtain an aqueous dispersion G containing silica particles having an amino group.
３．２．化学機械研磨用組成物の調製
酸化剤として過酸化水素（富士フイルム和光純薬株式会社製、３０％水溶液）を用い、ポリエチレン製容器に、表１〜表３に示す組成となるように各成分を添加し、さらに水酸化カリウムを必要に応じて加えて表１〜表３に示すｐＨとなるように調整し、全成分の合計量が１００質量部となるように純水で調整することにより、各実施例及び各比較例の化学機械研磨用組成物を調製した。3.2. Preparation of composition for chemical mechanical polishing Using hydrogen peroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 30% aqueous solution) as an oxidizing agent, each component is placed in a polyethylene container so as to have the compositions shown in Tables 1 to 3. And then add potassium hydroxide as needed to adjust the pH to the pH shown in Tables 1 to 3, and adjust with pure water so that the total amount of all components is 100 parts by mass. , The chemical mechanical polishing compositions of each Example and each Comparative Example were prepared.
３．３．評価方法
３．３．１．研磨速度試験
上記で得られた化学機械研磨用組成物を用いて、直径１２インチのＣＶＤ−Ｗ膜３００ｎｍ付きウエハ又は直径１２インチのｐ−ＴＥＯＳ膜（シリコン酸化膜）３００ｎｍ付きウエハを被研磨体として、下記の研磨条件で６０秒間の化学機械研磨試験を行った。3.3. Evaluation method 3.3.1. Polishing rate test Using the chemical mechanical polishing composition obtained above, a wafer with a CVD-W film of 300 nm with a diameter of 12 inches or a wafer with a p-TEOS film (silicon oxide film) of 300 nm with a diameter of 12 inches is used as an object to be polished. As a result, a chemical mechanical polishing test was conducted for 60 seconds under the following polishing conditions.
＜研磨条件＞
・研磨装置：ＡＭＡＴ社製、型式「Ｒｅｆｌｅｘｉｏｎ ＬＫ」
・研磨パッド：富士紡ホールディングス株式会社製、「多硬質ポリウレタン製パッド；Ｈ８００−ｔｙｐｅ１（３−１Ｓ）７７５」
・化学機械研磨用組成物供給速度：３００ｍＬ／分
・定盤回転数：１００ｒｐｍ
・ヘッド回転数：９０ｒｐｍ
・ヘッド押し付け圧：２．５ｐｓｉ
・研磨速度（Å／分）＝（研磨前の膜の厚さ−研磨後の膜の厚さ）／研磨時間<Polishing conditions>
・ Polishing equipment: AMAT, model "Reflexion LK"
-Polishing pad: Fujibo Holdings, Inc., "Multi-hard polyurethane pad; H800-type1 (3-1S) 775"
・ Chemical mechanical polishing composition supply speed: 300 mL / min ・ Surface plate rotation speed: 100 rpm
・ Head rotation speed: 90 rpm
・ Head pressing pressure: 2.5psi
・ Polishing speed (Å / min) = (thickness of film before polishing-thickness of film after polishing) / polishing time
なお、タングステン膜の厚さは、抵抗率測定機（ケーエルエー・テンコール社製、型式「ＯｍｎｉＭａｐ ＲＳ１００」）により直流４探針法で抵抗を測定し、このシート抵抗値とタングステンの体積抵抗率から下記式によって算出した。
・膜の厚さ（Å）＝［タングステン膜の体積抵抗率（Ω・ｍ）÷シート抵抗値（Ω）］×１０１０ The thickness of the tungsten film is determined by measuring the resistance with a DC 4-probe method using a resistivity measuring machine (manufactured by KLA Tencor, model "OmniMap RS100"), and the sheet resistance value and the volume resistivity of tungsten are as follows. Calculated by the formula.
・ Film thickness (Å) = [Volume resistivity of tungsten film (Ω ・ m) ÷ Sheet resistance value (Ω)] × 10 10
研磨速度試験の評価基準は下記の通りである。タングステン膜の研磨速度結果、シリコン酸化膜の研磨速度結果、及びその評価結果を表１〜表３に併せて示す。
（評価基準）
・「Ａ」…タングステン研磨速度が１００Å／分以上かつｐ−ＴＥＯＳ研磨速度が２００Å／分以上である場合、両者の研磨速度が十分に大きいため、実際の半導体基板の研磨において他材料膜の研磨との速度バランスが容易に確保でき、実用的であるから良好「Ａ」と判断した。
・「Ｂ」…タングステン研磨速度が１００Å／分未満またはｐ−ＴＥＯＳ研磨速度２００Å／分未満である場合、両者もしくはいずれか一方の研磨速度が小さいため、実用困難であり不良「Ｂ」と判断した。The evaluation criteria for the polishing speed test are as follows. Tables 1 to 3 also show the results of the polishing rate of the tungsten film, the results of the polishing rate of the silicon oxide film, and the evaluation results thereof.
(Evaluation criteria)
"A" ... When the tungsten polishing speed is 100 Å / min or more and the p-TEOS polishing speed is 200 Å / min or more, the polishing speeds of both are sufficiently high, so that the polishing of other material films is performed in the actual polishing of the semiconductor substrate. It was judged to be good "A" because the speed balance with and was easily secured and it was practical.
"B" ... When the tungsten polishing rate is less than 100 Å / min or the p-TEOS polishing rate is less than 200 Å / min, it is difficult to put into practical use because the polishing rate of either or both is low, and it is judged to be defective "B". ..
３．３．２．欠陥評価
被研磨体である直径１２インチのｐ−ＴＥＯＳ膜付きウエハを、下記条件で２分間研磨を行った。
＜研磨条件＞
・研磨装置：ＡＭＡＴ社製、型式「Ｒｅｆｌｅｘｉｏｎ ＬＫ」
・研磨パッド：富士紡ホールディングス株式会社製、「多硬質ポリウレタン製パッド；Ｈ８００−ｔｙｐｅ１（３−１Ｓ）７７５」
・化学機械研磨用組成物供給速度：３００ｍＬ／分
・定盤回転数：１００ｒｐｍ
・ヘッド回転数：９０ｒｐｍ
・ヘッド押し付け圧：２．５ｐｓｉ3.3.2. Defect evaluation A wafer with a p-TEOS film having a diameter of 12 inches, which is the object to be polished, was polished for 2 minutes under the following conditions.
<Polishing conditions>
・ Polishing equipment: AMAT, model "Reflexion LK"
-Polishing pad: Fujibo Holdings, Inc., "Multi-hard polyurethane pad; H800-type1 (3-1S) 775"
・ Chemical mechanical polishing composition supply speed: 300 mL / min ・ Surface plate rotation speed: 100 rpm
・ Head rotation speed: 90 rpm
・ Head pressing pressure: 2.5psi
上記で研磨が行われたｐ−ＴＥＯＳ膜付きウエハについて、欠陥検査装置（ケーエルエー・テンコール社製、型式「Ｓｕｒｆｓｃａｎ ＳＰ１」）を用いて、９０ｎｍ以上の大きさの欠陥総数をカウントした。評価基準は以下の通りである。ウエハ当たりの欠陥総数及びその評価結果を表１〜表３に併せて示す。
（評価基準）
・「Ａ」…ウエハ当たりの欠陥総数が５００個未満である場合を良好「Ａ」と判断した。
・「Ｂ」…ウエハ当たりの欠陥総数が５００個以上である場合を不良「Ｂ」と判断した。With respect to the wafer with the p-TEOS film polished above, the total number of defects having a size of 90 nm or more was counted using a defect inspection device (manufactured by KLA Tencor Co., Ltd., model “Surfscan SP1”). The evaluation criteria are as follows. The total number of defects per wafer and the evaluation results thereof are also shown in Tables 1 to 3.
(Evaluation criteria)
“A”: When the total number of defects per wafer is less than 500, it is judged as good “A”.
"B" ... When the total number of defects per wafer is 500 or more, it is determined to be defective "B".
３．４．評価結果
下表１〜下表３に、各実施例及び各比較例の化学機械研磨用組成物の組成並びに各評価結果を示す。3.4. Evaluation Results Tables 1 to 3 below show the composition of the chemical mechanical polishing composition of each example and each comparative example, and each evaluation result.
上表１〜上表３中の各成分は、それぞれ下記の商品又は試薬を用いた。なお、上表１〜上表３中の砥粒の含有量は、各水分散体の固形分濃度を表す。
＜砥粒＞
・水分散体Ａ〜Ｇ：上記で調製したシリカ粒子の水分散体Ａ〜Ｇ
・ＰＬ−３：扶桑化学工業株式会社製、商品名「ＰＬ−３」、コロイダルシリカ、平均粒子径７０ｎｍ
＜水酸基及びエーテル基を有する化合物＞
・ブチルカルビトール：東京化成工業株式会社製、商品名「Ｄｉｅｔｈｙｌｅｎｅ Ｇｌｙｃｏｌ Ｍｏｎｏｂｕｔｙｌ Ｅｔｈｅｒ」
・メチルカルビトール：東京化成工業株式会社製、商品名「Ｄｉｅｔｈｙｌｅｎｅ Ｇｌｙｃｏｌ Ｍｏｎｏｍｅｔｈｙｌ Ｅｔｈｅｒ （ｓｔａｂｉｌｉｚｅｄ ｗｉｔｈ ＢＨＴ）」
・エチルカルビトール：東京化成工業株式会社製、商品名「Ｄｉｅｔｈｙｌｅｎｅ Ｇｌｙｃｏｌ Ｍｏｎｏｅｔｈｙｌ Ｅｔｈｅｒ」
・ジプロピレングリコールモノメチルエーテル：東京化成工業株式会社製、商品名「Ｄｉｐｒｏｐｙｌｅｎｅ Ｇｌｙｃｏｌ Ｍｏｎｏｍｅｔｈｙｌ Ｅｔｈｅｒ （ｍｉｘｔｕｒｅ ｏｆ ｉｓｏｍｅｒｓ）」
＜有機酸＞
・クエン酸：東京化成工業株式会社製、商品名「Ｃｉｔｒｉｃ Ａｃｉｄ」
・マレイン酸：東京化成工業株式会社製、商品名「Ｍａｌｅｉｃ Ａｃｉｄ」
・マロン酸：東京化成工業株式会社製、商品名「Ｍａｌｏｎｉｃ Ａｃｉｄ」
・リンゴ酸：東京化成工業株式会社製、商品名「ＤＬ−Ａｐｐｌｅ Ａｃｉｄ」
・ヒスチジン：東京化成工業株式会社製、商品名「Ｌ−Ｈｉｓｔｉｄｉｎｅ」
・アルギニン：東京化成工業株式会社製、商品名「Ｌ−（＋）−Ａｒｇｉｎｉｎｅ」
＜水溶性高分子＞
・ポリアクリル酸：東亜合成株式会社製、商品名「ジュリマーＡＣ−１０Ｌ」、Ｍｗ＝２０，０００〜３０，０００
＜ｐＨ調整剤＞
・モノエタノールアミン：東京化成工業株式会社製、商品名「２−Ａｍｉｎｏｅｔｈａｎｏｌ」
・ＴＥＡＨ：東京化成工業株式会社製、商品名「Ｔｅｔｒａｅｔｈｙｌａｍｍｏｎｉｕｍ Ｈｙｄｒｏｘｉｄｅ（１０％ ｉｎ Ｗａｔｅｒ）」、テトラエチルアンモニウムヒドロキシドThe following products or reagents were used for each component in Tables 1 to 3 above. The content of the abrasive grains in the above tables 1 to 3 represents the solid content concentration of each aqueous dispersion.
<Abrasion grain>
Water dispersions A to G: Water dispersions A to G of silica particles prepared above.
-PL-3: Made by Fuso Chemical Industry Co., Ltd., trade name "PL-3", colloidal silica, average particle size 70 nm
<Compounds with hydroxyl groups and ether groups>
-Butyl carbitol: Made by Tokyo Chemical Industry Co., Ltd., trade name "Diethylene Glycol Monobutyl Ether"
-Methyl carbitol: Made by Tokyo Chemical Industry Co., Ltd., Product name "Diethylene Glycol Monomethyl Ether (stabilized with BHT)"
-Ethyl carbitol: Made by Tokyo Chemical Industry Co., Ltd., trade name "Diethylene Glycol Monoethyl Ether"
-Dipropylene glycol monomethyl ether: manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Dipylene Glycol Monomethyl Ether (mixture of isomers)"
<Organic acid>
-Citric acid: Made by Tokyo Chemical Industry Co., Ltd., product name "Citrus Acid"
-Maleic acid: Made by Tokyo Chemical Industry Co., Ltd., product name "Maleic Acid"
・ Malonic acid: Made by Tokyo Chemical Industry Co., Ltd., trade name "Malonic Acid"
-Malic acid: Made by Tokyo Chemical Industry Co., Ltd., Product name "DL-Apple Acid"
-Histidine: Made by Tokyo Chemical Industry Co., Ltd., product name "L-Histidine"
-Arginine: Made by Tokyo Chemical Industry Co., Ltd., Product name "L- (+)-Arginine"
<Water-soluble polymer>
-Polyacrylic acid: manufactured by Toagosei Co., Ltd., trade name "Julimer AC-10L", Mw = 20,000 to 30,000
<pH adjuster>
-Monoethanolamine: manufactured by Tokyo Chemical Industry Co., Ltd., product name "2-Aminoethanol"
-TEAH: Made by Tokyo Chemical Industry Co., Ltd., trade name "Tetraethylammonium Hydroxide (10% in Water)", tetraethylammonium hydroxide
実施例１〜２６の化学機械研磨用組成物を用いた場合には、いずれもタングステン膜及びｐ−ＴＥＯＳ膜を実用的な研磨速度で研磨することができ、かつ、研磨後におけるｐ−ＴＥＯＳ膜の表面欠陥の発生を低減することができた。 When the chemical mechanical polishing compositions of Examples 1 to 26 were used, the tungsten film and the p-TEOS film could be polished at a practical polishing rate, and the p-TEOS film after polishing could be used. It was possible to reduce the occurrence of surface defects.
本発明は、上述した実施形態に限定されるものではなく、種々の変形が可能である。例えば、本発明は、実施形態で説明した構成と実質的に同一の構成（例えば、機能、方法及び結果が同一の構成、あるいは目的及び効果が同一の構成）を含む。また、本発明は、実施形態で説明した構成の本質的でない部分を置き換えた構成を含む。また、本発明は、実施形態で説明した構成と同一の作用効果を奏する構成又は同一の目的を達成することができる構成を含む。また、本発明は、実施形態で説明した構成に公知技術を付加した構成を含む。 The present invention is not limited to the above-described embodiment, and various modifications are possible. For example, the present invention includes substantially the same configurations as those described in the embodiments (eg, configurations with the same function, method and result, or configurations with the same purpose and effect). The present invention also includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. Further, the present invention includes a configuration having the same action and effect as the configuration described in the embodiment or a configuration capable of achieving the same object. Further, the present invention includes a configuration in which a known technique is added to the configuration described in the embodiment.
１０…基体、１２…シリコン酸化膜、１４…ヴィアホール、１６…バリアメタル膜、１８…タングステン膜、４２…スラリー供給ノズル、４４…化学機械研磨用組成物（スラリー）、４６…研磨布、４８…ターンテーブル、５０…半導体基板、５２…キャリアーヘッド、５４…水供給ノズル、５６…ドレッサー、１００…被処理体、２００…半導体装置、３００…化学機械研磨装置 10 ... substrate, 12 ... silicon oxide film, 14 ... via hole, 16 ... barrier metal film, 18 ... tungsten film, 42 ... slurry supply nozzle, 44 ... chemical mechanical polishing composition (slurry), 46 ... polishing cloth, 48. ... turntable, 50 ... semiconductor substrate, 52 ... carrier head, 54 ... water supply nozzle, 56 ... dresser, 100 ... object to be treated, 200 ... semiconductor device, 300 ... chemical mechanical polishing device
Claims (10)
（Ｂ）水酸基及びエーテル基を有する化合物と、
を含有する、化学機械研磨用組成物。
−ＣＯＯ−Ｍ＋ ・・・・・（１）
（Ｍ＋は１価の陽イオンを表す。）(A) Silica particles having a functional group represented by the following general formula (1) and
(B) A compound having a hydroxyl group and an ether group, and
A composition for chemical mechanical polishing containing.
-COO - M + ... (1)
(M + represents a monovalent cation.)
前記（Ａ）成分の含有量が０．１質量％以上１０質量％以下であり、
前記（Ｂ）成分の含有量が０．０００１質量％以上０．０５質量％以下である、請求項１に記載の化学機械研磨用組成物。When the total mass of the chemical mechanical polishing composition is 100% by mass,
The content of the component (A) is 0.1% by mass or more and 10% by mass or less.
The composition for chemical mechanical polishing according to claim 1, wherein the content of the component (B) is 0.0001% by mass or more and 0.05% by mass or less.
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