JP6030145B2 - Polishing slurry and substrate polishing method using the same - Google Patents
Polishing slurry and substrate polishing method using the same Download PDFInfo
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- JP6030145B2 JP6030145B2 JP2014539865A JP2014539865A JP6030145B2 JP 6030145 B2 JP6030145 B2 JP 6030145B2 JP 2014539865 A JP2014539865 A JP 2014539865A JP 2014539865 A JP2014539865 A JP 2014539865A JP 6030145 B2 JP6030145 B2 JP 6030145B2
- Authority
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- Prior art keywords
- slurry
- polishing
- content
- tungsten
- titanium oxide
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims description 158
- 239000002002 slurry Substances 0.000 title claims description 114
- 238000000034 method Methods 0.000 title description 38
- 239000000758 substrate Substances 0.000 title description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 109
- 239000010937 tungsten Substances 0.000 claims description 91
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 89
- 229910052721 tungsten Inorganic materials 0.000 claims description 86
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 71
- 239000002245 particle Substances 0.000 claims description 65
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 33
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 20
- 239000007800 oxidant agent Substances 0.000 claims description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011164 primary particle Substances 0.000 claims description 8
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 3
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 3
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 3
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- -1 potassium ferricyanide Chemical compound 0.000 claims description 3
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 3
- 239000001230 potassium iodate Substances 0.000 claims description 3
- 229940093930 potassium iodate Drugs 0.000 claims description 3
- 235000006666 potassium iodate Nutrition 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 50
- 229910001930 tungsten oxide Inorganic materials 0.000 description 36
- 229910052814 silicon oxide Inorganic materials 0.000 description 34
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 31
- 230000003628 erosive effect Effects 0.000 description 21
- 238000007517 polishing process Methods 0.000 description 14
- 239000008119 colloidal silica Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
-
- 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
- C09K3/1409—Abrasive particles per se
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/7684—Smoothing; Planarisation
Description
本発明は、金属を研磨する工程において用いられる研磨用スラリー及びこれを用いた研磨方法に関する。さらに詳しくは、半導体製造工程のうち、化学機械的な研磨工程において用いられる、特に、タングステン金属膜の平坦化に使用可能なスラリー及びこれを用いた研磨方法に関する。 The present invention relates to a polishing slurry used in a step of polishing a metal and a polishing method using the same. More particularly, the present invention relates to a slurry that can be used for planarizing a tungsten metal film, and a polishing method using the same, used in a chemical mechanical polishing process in a semiconductor manufacturing process.
半導体素子のサイズが益々縮小され、且つ、金属配線層の数が益々増大されるにつれて、各層における表面うねりは次の層に転写されて最下層表面のうねり度が重要視されつつある。このようなうねりは、次のステップにおいて所望の形状を形成し難い程度に深刻な影響を及ぼすことがある。したがって、半導体素子の歩留まりを向上させるためには、例えば、半導体製造工程中における配線抵抗のばらつきを低減するために複数の工程中に発生する不規則的な表面うねりを除去する平坦化工程が必ず用いられている。 As the size of semiconductor elements is further reduced and the number of metal wiring layers is increased, the surface undulation in each layer is transferred to the next layer, and the degree of undulation on the lowermost layer surface is becoming more important. Such undulation may have a serious effect on the extent to which it is difficult to form the desired shape in the next step. Therefore, in order to improve the yield of semiconductor elements, for example, a flattening process for removing irregular surface waviness that occurs in a plurality of processes in order to reduce variations in wiring resistance during the semiconductor manufacturing process is necessarily performed. It is used.
平坦化方法としては、蒸着膜を形成した後にリフローさせる方法、蒸着膜を形成した後にエッチバックする方法または化学機械的な研磨（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ；以下、ＣＭＰと称する。）方法など種々の方法が挙げられる。 As a planarization method, various methods such as a method of performing reflow after forming a deposited film, a method of etching back after forming a deposited film, or a chemical mechanical polishing (hereinafter referred to as CMP) method are used. Can be mentioned.
ＣＭＰ工程とは、半導体ウェーハの表面を研磨パッドに押し当てて回転運動を行いながら、研磨剤と各種の化合物が含有されたスラリーを提供して平らに研磨する工程をいう。すなわち、基板やその上部の層の表面がスラリー及び研磨パッドによって機械的及び化学的に研磨されて平坦化される。一般的に、金属を研磨する金属ＣＭＰ工程は、酸化剤によって金属酸化物が形成される過程と、形成された金属酸化物を研磨剤が除去する過程とが繰り返し行われることが知られている。 The CMP process refers to a process in which a slurry containing an abrasive and various compounds is provided and polished flatly while pressing the surface of the semiconductor wafer against a polishing pad and performing a rotational motion. That is, the surface of the substrate and the upper layer thereof is mechanically and chemically polished and planarized by the slurry and the polishing pad. In general, it is known that a metal CMP process for polishing a metal includes a process in which a metal oxide is formed by an oxidizing agent and a process in which the abrasive removes the formed metal oxide. .
半導体素子の配線として多用されるタングステンを研磨するタングステンＣＭＰ工程も、酸化剤もしくは酸化促進剤によってタングステン酸化物（ＷＯ３）が形成される過程と、研磨剤によってタングステン酸化物が除去される過程とが繰り返し行われる循環研磨メカニズムによって研磨が行われる。このため、研磨率を向上させるためには酸化剤を添加してタングステン酸化物を形成し、研磨剤によってタングステン酸化物を効率よく除去することが重要である。しかしながら、既存に汎用される研磨剤であるコロイダルシリカの場合、タングステン酸化物を除去するに際して酸化剤濃度依存性が高いため非効率的である。なお、トレンチなどパターンが形成された基板を研磨する場合にはディッシングやエロージョンなどの欠陥が頻発するという問題がある。このようなディッシングやエロージョンが生じる場合、今後製造される素子が誤作動するなど素子の動作特性に悪影響を及ぼしてしまう。 A tungsten CMP process for polishing tungsten, which is frequently used as a wiring of a semiconductor element, includes a process in which tungsten oxide (WO 3 ) is formed by an oxidizing agent or an oxidation accelerator, and a process in which tungsten oxide is removed by an abrasive. Polishing is performed by a cyclic polishing mechanism that is repeatedly performed. For this reason, in order to improve the polishing rate, it is important to add an oxidizing agent to form tungsten oxide and efficiently remove the tungsten oxide with the polishing agent. However, in the case of colloidal silica, which is an existing widely used abrasive, it is inefficient because it has high oxidant concentration dependency when removing tungsten oxide. In the case of polishing a substrate on which a pattern such as a trench is formed, there is a problem that defects such as dishing and erosion frequently occur. When such dishing or erosion occurs, an element manufactured in the future malfunctions, which adversely affects the operation characteristics of the element.
一方、大韓民国特許公報第１０−０９４８８１４号には、ディッシング及びエロージョンを低減するために、２段階に亘って研磨を行う方法が開示されているが、この場合、複数のスラリーを用意し、複数の工程を行うことを余儀なくされるため工程が複雑になり、しかも、生産性が低下するという問題が引き起こされる。 On the other hand, Korean Patent Publication No. 10-094814 discloses a method of polishing in two stages in order to reduce dishing and erosion. In this case, a plurality of slurries are prepared, Since the process is inevitably performed, the process becomes complicated, and the problem that productivity decreases is caused.
本発明の目的は、タングステン研磨用スラリー及びこれを用いた基板の研磨方法を提供することである。 An object of the present invention is to provide a slurry for polishing tungsten and a method for polishing a substrate using the same.
本発明の他の目的は、タングステン研磨率及びタングステンと絶縁膜の研磨選択比に優れたタングステン研磨用スラリー及びこれを用いた基板の研磨方法を提供することである。 Another object of the present invention is to provide a tungsten polishing slurry excellent in tungsten polishing rate and polishing selectivity between tungsten and an insulating film, and a substrate polishing method using the same.
本発明のさらに他の目的は、研磨工程中に発生するディッシングとエロージョンを低減するタングステン研磨用スラリー及びこれを用いた基板の研磨方法を提供することである。 Still another object of the present invention is to provide a tungsten polishing slurry that reduces dishing and erosion generated during the polishing process, and a substrate polishing method using the same.
本発明の一実施形態に係るスラリーは、タングステン研磨用スラリーであって、研磨を行う研磨剤及び酸化物形成を促す酸化促進剤を含み、前記研磨剤として酸化チタン粒子を含む。 A slurry according to an embodiment of the present invention is a tungsten polishing slurry, which includes a polishing agent for polishing and an oxidation accelerator for promoting oxide formation, and includes titanium oxide particles as the polishing agent.
前記酸化チタンの含量は、スラリーの総重量に対して、約０．２重量％超え約１０重量％以下であってもよい。 The titanium oxide content may be more than about 0.2% by weight and about 10% by weight or less based on the total weight of the slurry.
前記酸化促進剤として、硝酸鉄、フェリシアン化カリウム、塩化鉄、硫酸鉄、フッ化鉄、臭化鉄、塩化銅、フッ化銅及び臭化銅よりなる群から選ばれた少なくとも一種を含んでいてもよく、前記酸化促進剤の含量は、スラリーの総重量に対して、約０．００２重量％以上約０．１重量％以下であってもよい。 The oxidation accelerator may include at least one selected from the group consisting of iron nitrate, potassium ferricyanide, iron chloride, iron sulfate, iron fluoride, iron bromide, copper chloride, copper fluoride, and copper bromide. The content of the oxidation accelerator may be about 0.002 wt% or more and about 0.1 wt% or less based on the total weight of the slurry.
前記酸化チタンの含量は、スラリーの総重量に対して、約０．７〜約５重量％であってもよい。 The titanium oxide content may be about 0.7 to about 5% by weight based on the total weight of the slurry.
前記酸化促進剤の含量は、スラリーの総重量に対して、約０．０１重量％以上約０．１重量％以下であってもよい。 The content of the oxidation accelerator may be about 0.01 wt% or more and about 0.1 wt% or less based on the total weight of the slurry.
前記スラリーは、ｐＨが約１〜約４に調節されてもよい。 The slurry may be adjusted to a pH of about 1 to about 4.
酸化物を形成する酸化剤として、過酸化水素水、過酸化尿素、過硫酸アンモニウム、チオ硫酸アンモニウム、次亜塩素酸ナトリウム、過ヨウ素酸ナトリウム、過硫酸ナトリウム 、ヨウ素酸カリウム、過塩素酸カリウム及び過硫酸カリウムよりなる群から選ばれた少なくとも一種を含んでいてもよく、前記酸化剤の含量は、スラリーの総重量に対して、約０．５重量％以上約５．０重量％未満であってもよい。 As oxidizing agents that form oxides, hydrogen peroxide, urea peroxide, ammonium persulfate, ammonium thiosulfate, sodium hypochlorite, sodium periodate, sodium persulfate, potassium iodate, potassium perchlorate and persulfate It may contain at least one selected from the group consisting of potassium, and the content of the oxidizing agent may be about 0.5 wt% or more and less than about 5.0 wt% with respect to the total weight of the slurry. Good.
前記酸化剤の含量は、スラリーの総重量に対して、約０．５重量％〜約２重量％であってもよい。 The oxidant content may be about 0.5 wt% to about 2 wt% based on the total weight of the slurry.
選択比向上剤として、ポリビニールピロリドン、ビニールピリジン及びビニールピロリドンよりなる群から選ばれた少なくとも一種を含んでいてもよい。 As the selection ratio improver, at least one selected from the group consisting of polyvinyl pyrrolidone, vinyl pyridine and vinyl pyrrolidone may be included.
前記選択比向上剤の含量は、スラリーの総重量に対して、約０．０５重量％以上約３．０重量％未満であってもよい。 The selection ratio improver may be about 0.05 wt% or more and less than about 3.0 wt% based on the total weight of the slurry.
前記酸化チタン粒子は結晶相に形成されてもよく、平均１次粒子径が約１０ｎｍ〜約１００ｎｍであってもよい。 The titanium oxide particles may be formed in a crystalline phase, and the average primary particle size may be about 10 nm to about 100 nm.
本発明の他の実施形態に係るスラリーは、タングステン研磨用スラリーであって、研磨を行う研磨剤として酸化チタン粒子を含み、前記酸化チタン粒子は結晶相に形成され、少なくとも一部はアナターゼ結晶相に形成され、前記酸化チタン粒子は、平均１次粒子径が約１０ｎｍ〜約１００ｎｍである。 A slurry according to another embodiment of the present invention is a slurry for polishing tungsten, and includes titanium oxide particles as an abrasive for polishing, wherein the titanium oxide particles are formed in a crystalline phase, and at least a part of the anatase crystalline phase The titanium oxide particles have an average primary particle diameter of about 10 nm to about 100 nm.
前記酸化チタン粒子は、多面体状を呈していてもよい。 The titanium oxide particles may have a polyhedral shape.
前記酸化チタン粒子は、平均１次粒子径が約１５ｎｍ以上約５０ｎｍ未満であってもよい。 The titanium oxide particles may have an average primary particle size of about 15 nm or more and less than about 50 nm.
前記酸化チタン粒子は、アナターゼ相とルチル相を有し、前記アナターゼ相とルチル相の総和を１００としたとき、前記アナターゼ相が約５０を超えてもよい。 The titanium oxide particles have an anatase phase and a rutile phase, and when the sum of the anatase phase and the rutile phase is 100, the anatase phase may exceed about 50.
前記酸化チタンの含量は、スラリーの総重量に対して、約０．２重量％超え約１０重量％以下であってもよい。 The titanium oxide content may be more than about 0.2% by weight and about 10% by weight or less based on the total weight of the slurry.
前記スラリーは、酸化物の形成を促す酸化促進剤を含んでいてもよく、前記スラリーは、ｐＨ調節剤を含んでいてもよい。 The slurry may contain an oxidation accelerator that promotes oxide formation, and the slurry may contain a pH adjuster.
本発明のさらに他の実施形態に係る基板の研磨方法は、タングステン層が形成された基板を設ける過程と、研磨剤としての酸化チタン粒子と酸化促進剤を含む１次スラリーを設ける過程と、前記１次スラリーを前記基板の上に供給しながら前記タングステン層を研磨する過程と、を含み、前記研磨過程においては、前記タングステン層の上部表面にタングステン酸化膜が形成され、前記酸化チタン粒子の少なくとも一部が前記タングステン酸化膜の内部に浸透して前記タングステン層及び前記タングステン酸化膜を研磨する。 A method for polishing a substrate according to still another embodiment of the present invention includes a step of providing a substrate on which a tungsten layer is formed, a step of providing a primary slurry containing titanium oxide particles and an oxidation accelerator as an abrasive, Polishing the tungsten layer while supplying a primary slurry onto the substrate. In the polishing process, a tungsten oxide film is formed on the upper surface of the tungsten layer, and at least the titanium oxide particles A part penetrates into the tungsten oxide film to polish the tungsten layer and the tungsten oxide film.
前記１次スラリーを前記基板の上に供給しながら酸化剤を前記基板の上に供給してもよい。 The oxidant may be supplied onto the substrate while the primary slurry is supplied onto the substrate.
前記１次スラリーを前記基板の上に供給しながら選択比向上剤を前記基板の上に供給してもよい。 The selection ratio improver may be supplied onto the substrate while the primary slurry is supplied onto the substrate.
前記選択比向上剤または前記酸化剤は、前記１次スラリーとは別途の流入ラインを介して前記基板の上に提供されてもよい。 The selectivity improver or the oxidizer may be provided on the substrate through an inflow line separate from the primary slurry.
前記酸化促進剤は硝酸鉄を含んでいてもよく、前記酸化剤は過酸化水素水であってもよい。 The oxidation accelerator may contain iron nitrate, and the oxidizing agent may be hydrogen peroxide.
前記研磨過程が行われる間に前記タングステン酸化膜は所定の膜厚に保たれてもよい。 The tungsten oxide film may be maintained at a predetermined film thickness during the polishing process.
前記研磨過程が行われる間に前記酸化チタン粒子の少なくとも一部は前記タングステン層表面と直接的に接触してもよい。 During the polishing process, at least a part of the titanium oxide particles may be in direct contact with the tungsten layer surface.
前記タングステン層が形成された基板を設ける過程においては、前記基板の上に絶縁膜を形成し、前記絶縁膜にトレンチを形成し、前記トレンチを含む絶縁膜の全面にタングステン層を形成してもよい。 In the process of providing the substrate on which the tungsten layer is formed, an insulating film is formed on the substrate, a trench is formed in the insulating film, and a tungsten layer is formed on the entire surface of the insulating film including the trench. Good.
本発明の実施形態によれば、研磨剤として酸化チタンを用いることにより、タングステンを直接的に接触して研磨することができて、タングステン研磨率が大幅に向上され、タングステンと絶縁膜の研磨選択比に優れた研磨工程を行うことができる。 According to the embodiment of the present invention, by using titanium oxide as an abrasive, tungsten can be directly contacted and polished, the tungsten polishing rate is greatly improved, and the selection of polishing of tungsten and insulating film A polishing process having an excellent ratio can be performed.
本発明の実施形態に係るスラリーは、従来の循環研磨に際して発生するディッシング及びエロージョンを大幅に低減することができる。特に、ディッシングがほとんど発生しない研磨工程を実現することができる。 The slurry according to the embodiment of the present invention can greatly reduce dishing and erosion that occur during conventional cyclic polishing. In particular, it is possible to realize a polishing process in which dishing hardly occurs.
さらに、本発明の実施形態に係るスラリーは、製造し易く、ＣＭＰ工程を単純に行うことができてタングステンを効率よく研磨することができ、その結果、半導体素子の動作特性及び信頼性を向上させることができ、製造生産性も向上させることができる。 Furthermore, the slurry according to the embodiment of the present invention is easy to manufacture, can perform the CMP process simply, can polish tungsten efficiently, and as a result, improves the operating characteristics and reliability of the semiconductor device. Manufacturing productivity can also be improved.
以下、添付図面に基づき、本発明の実施形態を詳述する。しかしながら、本発明は、後述する実施形態に何ら限定されるものではなく、異なる種々の形態で実現される。単に、これらの実施形態は、本発明の開示を完全たるものにし、本発明の属する技術の分野における通常の知識を有する者に発明の範囲を完全に知らせるために提供されるものである。図中、同じ符号は同じ構成要素を示す。 Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described below, and can be realized in various different forms. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art to which this invention belongs. In the drawings, the same reference numerals indicate the same components.
本発明の実施形態に係るスラリーは、タングステン研磨用スラリーであって、研磨を行う研磨剤及び酸化物形成を促す酸化促進剤を含み、研磨剤として酸化チタン粒子を含む。研磨剤と酸化促進剤は溶液中に含有される。すなわち、水、特に、超純水（ＤＩ ｗａｔｅｒ）に酸化促進剤が溶解され、研磨剤が分散されて分布する。なお、スラリーのｐＨを調節するためにｐＨ調節剤をさらに含んでいてもよい。このようなスラリーは、液体に固体（研磨剤）が分散された形であり、各成分の含量が適切に調節される。 The slurry according to the embodiment of the present invention is a slurry for polishing tungsten, includes a polishing agent for polishing and an oxidation accelerator for promoting oxide formation, and includes titanium oxide particles as the polishing agent. An abrasive and an oxidation accelerator are contained in the solution. That is, the oxidation accelerator is dissolved in water, particularly ultrapure water (DI water), and the abrasive is dispersed and distributed. In addition, in order to adjust pH of a slurry, the pH adjuster may be further included. Such a slurry is in a form in which a solid (abrasive) is dispersed in a liquid, and the content of each component is appropriately adjusted.
一方、スラリーは、前記成分を含む１次スラリー及びその他の成分を研磨を行う工程に際して別途に用いることができる。すなわち、前記１次スラリーとは別途の容器に保管される酸化剤及び選択比向上剤をさらに含んでいてもよい。 On the other hand, the slurry can be used separately in the step of polishing the primary slurry containing the components and other components. That is, the primary slurry may further contain an oxidizing agent and a selectivity improving agent stored in a separate container.
先ず、研磨剤としての酸化チタンは固体粒子であって、多面体状の結晶相に形成される。酸化チタンは、金属チタンの酸化物であって、特に、二酸化チタン（ＴｉＯ２）を含む。図１の透過電子顕微鏡（ｔｒａｎｓｍｉｓｓｉｏｎ ｅｌｅｃｔｒｏｎｍｉｃｒｏｓｃｏｐｅ：ＴＥＭ）写真から明らかなように、従来研磨剤として主に用いられるシリカの場合、非晶質相であり、粒子の形状が球状であるが（図１のａ、ｂ）、酸化チタン研磨粒子は結晶質相であり、結晶面を有する多面体状である（図１のｃ、ｄ）。酸化チタン研磨粒子をＸ線回折分析した図２からも、酸化チタン研磨粒子が結晶相として存在することが分かる。このように酸化チタン研磨粒子が結晶相であり、結晶面を有することにより、タングステン研磨を効率よく行うことができる。これについては、後述する。 First, titanium oxide as an abrasive is solid particles and is formed into a polyhedral crystal phase. Titanium oxide is an oxide of titanium metal, and particularly includes titanium dioxide (TiO 2 ). As is apparent from the transmission electron microscope (TEM) photograph of FIG. 1, in the case of silica, which is mainly used as a conventional abrasive, it is an amorphous phase and the particle shape is spherical (see FIG. 1). a, b) The titanium oxide abrasive particles are in a crystalline phase and are polyhedral with crystal faces (c, d in FIG. 1). 2 that X-ray diffraction analysis of the titanium oxide abrasive particles also shows that the titanium oxide abrasive particles exist as a crystal phase. As described above, the titanium oxide abrasive particles are in a crystalline phase and have a crystal face, so that tungsten polishing can be efficiently performed. This will be described later.
酸化チタン研磨粒子は、平均１次粒子の粒径を約１０ｎｍ〜約１００ｎｍにする。酸化チタン研磨粒子の平均粒径が約１０ｎｍよりも小さな場合に研磨率が低くてタングステン研磨が行い難く、約１００ｎｍよりも大きな場合には研磨に際して傷つきが発生する。なお、酸化チタン研磨粒子の平均１次粒子の粒径が約１５ｎｍ以上約５０ｎｍ未満であることが好ましい。この範囲において研磨粒子の濃度が最適化されて高い研磨率を達成しながら傷つきの発生を極力抑えることができる。 The titanium oxide abrasive particles have an average primary particle size of about 10 nm to about 100 nm. When the average particle diameter of the titanium oxide abrasive particles is smaller than about 10 nm, the polishing rate is low and tungsten polishing is difficult to perform, and when the average particle diameter is larger than about 100 nm, scratching occurs during the polishing. The average primary particle size of the titanium oxide abrasive particles is preferably about 15 nm or more and less than about 50 nm. In this range, the concentration of the abrasive particles is optimized, and the occurrence of scratches can be suppressed as much as possible while achieving a high polishing rate.
また、酸化チタン研磨粒子は少なくとも一部がアナターゼ結晶相を有し、他の結晶相に比べてアナターゼがさらに多く含まれることが好ましい。すなわち、酸化チタン研磨粒子はアナターゼ相とルチル相を有し、アナターゼ相がルチル相よりも多量含まれることが好ましい。特に、酸化チタン研磨粒子は、アナターゼ相とルチル相の総和を１００としたとき、アナターゼ相が５５以上であることが好ましい。通常、酸化チタンとしては、結晶構造が異なる３つの変種が知られているが、高温において安定したルチル型、低温において安定したアナターゼ型、中間温度において安定したブルカイト型がある。ルチル型は耐化学性に優れているため熱にも強いが、硬さが約６〜約６．５であって、アナターゼ型の硬さよりも高くて製造し難い。これに対し、アナターゼ型は製造し易く、硬さが約５．５〜約６であって、ルチル型の硬さよりも低い。一方、タングステン研磨時に表面に生成されるタングステン酸化膜の硬さは約５〜約６であり、タングステンの下部に存在する絶縁膜であるシリコン酸化膜の硬さは約６〜約７である。タングステン酸化膜とシリコン酸化膜の研磨率を向上させるためには研磨粒子の硬さが高いもの、すなわち、ルチル型であることが好ましいが、研磨剤がルチル型である場合、研磨率が高すぎ、傷つきが発生する。また、シリコン酸化膜が多量除去されてエロージョンが発生する虞がある。このため、ルチル型に比べて相対的に硬さが低いが、タングステン酸化膜を研磨するのに十分な硬さを有するアナターゼ型を含むことが好ましい。特に、アナターゼ型を約５５以上含む場合、傷つきの発生を顕著に低減し、シリコン酸化膜に対する研磨率を減らしてエロージョンの発生を抑えることができる。 Moreover, it is preferable that at least a part of the titanium oxide abrasive particles has an anatase crystal phase, and more anatase is contained than other crystal phases. That is, the titanium oxide abrasive particles preferably have an anatase phase and a rutile phase, and the anatase phase is preferably contained in a larger amount than the rutile phase. In particular, the titanium oxide abrasive particles preferably have an anatase phase of 55 or more when the sum of the anatase phase and the rutile phase is 100. In general, three types of titanium oxide having different crystal structures are known. There are a rutile type that is stable at high temperatures, an anatase type that is stable at low temperatures, and a brookite type that is stable at intermediate temperatures. Since the rutile type is excellent in chemical resistance and resistant to heat, the hardness is about 6 to about 6.5, which is higher than the anatase type hardness and difficult to manufacture. On the other hand, the anatase type is easy to manufacture and has a hardness of about 5.5 to about 6, which is lower than the rutile type. On the other hand, the hardness of the tungsten oxide film formed on the surface during tungsten polishing is about 5 to about 6, and the hardness of the silicon oxide film, which is an insulating film existing under tungsten, is about 6 to about 7. In order to improve the polishing rate of the tungsten oxide film and the silicon oxide film, it is preferable that the abrasive particles have a high hardness, that is, a rutile type, but if the abrasive is a rutile type, the polishing rate is too high. , Scratches occur. In addition, a large amount of the silicon oxide film may be removed and erosion may occur. For this reason, it is preferable to include an anatase type having a relatively low hardness as compared with the rutile type, but having a hardness sufficient for polishing the tungsten oxide film. In particular, when about 55 or more anatase types are included, the occurrence of scratches can be remarkably reduced, and the polishing rate for the silicon oxide film can be reduced to suppress the occurrence of erosion.
また、酸化チタン研磨粒子の含量は、スラリーの総重量に対して、約０．２重量％超え約１０重量％以下であることが好ましい。酸化チタン研磨粒子の含量が約０．２重量％以下であれば、研磨率が低すぎて研磨し難く、酸化チタン研磨粒子の含量が約１０重量％を超えると、粒子の分散安定性に問題が発生し、二次粒子の粒径が過剰に大きくなってしまうという問題が発生する。酸化チタン研磨粒子の含量は、スラリーの総重量に対して、約０．７重量％〜約５重量％であることが好ましく、約１．０重量％〜約２．０重量％であることがさらに好ましい。これは、約０．７重量％〜約５重量％の範囲においてタングステン研磨率に優れていて分散安定性が確保されるためであり、約１．０重量％〜約２．０重量％の範囲においてはタングステン研磨率に一層優れているためである。 The content of titanium oxide abrasive particles is preferably more than about 0.2% by weight and about 10% by weight or less based on the total weight of the slurry. If the content of titanium oxide abrasive particles is about 0.2% by weight or less, the polishing rate is too low to be polished, and if the content of titanium oxide abrasive particles exceeds about 10% by weight, there is a problem in the dispersion stability of the particles. And the secondary particle size becomes excessively large. The content of titanium oxide abrasive particles is preferably about 0.7 wt% to about 5 wt%, and preferably about 1.0 wt% to about 2.0 wt%, based on the total weight of the slurry. Further preferred. This is because in the range of about 0.7 wt% to about 5 wt%, the tungsten polishing rate is excellent and dispersion stability is ensured, and in the range of about 1.0 wt% to about 2.0 wt%. This is because the tungsten polishing rate is more excellent.
酸化促進剤は、タングステン層の表面が酸化されることを促す成分であり、硝酸鉄（Ｆｅｒｒｉｃ ｎｉｔｒｉｄｅ、Ｆｅ（ＮＯ３）３））、フェリシアン化カリウム（Ｐｏｔａｓｓｉｕｍ ｆｅｒｒｉｃｙａｎｉｄｅ）、塩化鉄（Ｉｒｏｎ（III） ｃｈｌｏｒｉｄｅ）、硫酸鉄（Ｉｒｏｎ（III） ｓｕｌｆａｔｅ）、フッ化鉄（Ｉｒｏｎ（III） ｆｌｕｏｒｉｄｅ）、臭化鉄（Ｉｒｏｎ（III） ｂｒｏｍｉｄｅ）、塩化銅（Ｃｏｐｐｅｒ（II） ｃｈｌｏｒｉｄｅ）、フッ化銅（Ｃｏｐｐｅｒ（II） ｆｌｕｏｒｉｄｅ）及び臭化銅（Ｃｏｐｐｅｒ（II） ｂｒｏｍｉｄｅ）よりなる群から選ばれた少なくとも一種を含む。ここでは、主として硝酸鉄を用いる。酸化促進剤を用いなくても、タングステンを研磨することはできるが、その研磨率が非常に低い。酸化促進剤としての硝酸鉄は超純水に溶解されて存在し、スラリーの総重量に対して約０．００２重量％〜約０．１重量％で含まれることが好ましい。硝酸鉄の含量が約０．００２重量％よりも低ければ、研磨率が低すぎて研磨し難く、硝酸鉄の含量が約０．１重量％よりも高ければ、スラリー及び研磨パッドが変色するという問題が発生する。硝酸鉄の含量は、スラリーの総重量に対して、約０．０１重量％〜約０．１重量％であることが好ましく、約０．０５重量％〜約０．１重量％であることがさらに好ましい。これは、硝酸鉄の含量が約０．０１重量％〜約０．１重量％の範囲においてタングステン研磨率に優れており、約０．０５重量％〜約０．１重量％の範囲において最適な濃度を有してディッシングがあまり発生しないためである。 The oxidation accelerator is a component that promotes oxidation of the surface of the tungsten layer, and includes iron nitrate (Ferric nitride, Fe (NO 3 ) 3 ), potassium ferricyanide, iron chloride (Iron (III) chloride). ), Iron sulfate (Iron (III) sulfate), iron fluoride (Iron (III) fluoride), iron bromide (Iron (III) bromide), copper chloride (Copper (II) chloride), copper fluoride (Copper ( II) including at least one selected from the group consisting of fluoride) and copper bromide (Copper (II) bromide). Here, iron nitrate is mainly used. Tungsten can be polished without using an oxidation accelerator, but its polishing rate is very low. It is preferable that iron nitrate as an oxidation accelerator is present in a state of being dissolved in ultrapure water and contained at about 0.002 wt% to about 0.1 wt% with respect to the total weight of the slurry. If the iron nitrate content is lower than about 0.002% by weight, the polishing rate is too low to be polished, and if the iron nitrate content is higher than about 0.1% by weight, the slurry and the polishing pad are discolored. A problem occurs. The iron nitrate content is preferably about 0.01 wt% to about 0.1 wt%, and preferably about 0.05 wt% to about 0.1 wt%, based on the total weight of the slurry. Further preferred. This is excellent in tungsten polishing rate when the iron nitrate content is in the range of about 0.01 wt% to about 0.1 wt%, and is optimal in the range of about 0.05 wt% to about 0.1 wt%. This is because dishing does not occur so much with a density.
酸化剤はタングステン層の表面を酸化させる成分であり、過酸化水素水（Ｈ２Ｏ２）、過酸化尿素（Ｃａｒｂａｍｉｄｅ ｐｅｒｏｘｉｄｅ）、過硫酸アンモニウム（ａｍｍｏｎｉｕｍ ｐｅｒｓｕｌｆａｔｅ）、チオ硫酸アンモニウム（Ａｍｍｏｎｉｕｍ ｔｈｉｏｓｕｌｆａｔｅ）、次亜塩素酸ナトリウム（Ｓｏｄｉｕｍ ｈｙｐｏｃｈｌｏｒｉｔｅ）、過ヨウ素酸ナトリウム（Ｓｏｄｉｕｍ ｐｅｒｉｏｄａｔｅ）、過硫酸ナトリウム、ヨウ素酸カリウム（Ｐｏｔａｓｓｉｕｍ ｉｏｄａｔｅ）、過塩素酸カリウム（Ｐｏｔａｓｓｉｕｍ ｐｅｒｃｈｌｏｒａｔｅ）及び過硫酸カリウム（Ｐｏｔａｓｓｉｕｍ ｐｅｒｓｕｌｆａｔｅ）よりなる群から選ばれた少なくとも一種を含む。ここでは、主として過酸化水素水を用いる。酸化剤を用いなくてもタングステンを研磨することはできるが、その研磨率が非常に低い。酸化剤としての過酸化水素水の含量は、スラリーの総重量に対して、約０．５重量％以上約５．０重量％未満であることが好ましい。過酸化水素水の含量が約０．５重量％よりも低ければ、研磨率が低すぎて研磨し難く、過酸化水素水の含量が約５．０重量％以上であれば、バブルが生じ始める。過酸化水素水の含量は、スラリーの総重量に対して、約０．５重量％〜約２．０重量％であることが好ましく、約１重量％〜約２重量％であることがさらに好ましい。これは、過酸化水素水の含量が約０．５重量％〜約２．０重量％の範囲においてタングステン研磨率が適切であり、約１重量％〜約２重量％の範囲において最適な濃度を有してディッシングがあまり発生しないためである。酸化剤と酸化促進剤はその作用が明確に区別されないこともあり、両方ともタングステン層の表面を酸化させるのに寄与する。 The oxidizing agent is a component that oxidizes the surface of the tungsten layer, and includes hydrogen peroxide water (H 2 O 2 ), urea peroxide (Ammonium persulfate), ammonium persulfate, ammonium thiosulfate, hypochlorite. It is selected from the group consisting of sodium peroxide, sodium periodate, sodium persulfate, potassium iodate, potassium perchlorate and potassium persulfate. Including at least one kind. Here, hydrogen peroxide water is mainly used. Although tungsten can be polished without using an oxidizing agent, its polishing rate is very low. The content of the hydrogen peroxide solution as the oxidizing agent is preferably about 0.5 wt% or more and less than about 5.0 wt% based on the total weight of the slurry. If the hydrogen peroxide solution content is lower than about 0.5% by weight, the polishing rate is too low to be polished, and if the hydrogen peroxide solution content is about 5.0% by weight or more, bubbles start to form. . The content of the hydrogen peroxide solution is preferably about 0.5 wt% to about 2.0 wt%, more preferably about 1 wt% to about 2 wt%, based on the total weight of the slurry. . This is because the tungsten polishing rate is appropriate when the content of hydrogen peroxide is in the range of about 0.5 wt% to about 2.0 wt%, and the optimum concentration is obtained in the range of about 1 wt% to about 2 wt%. This is because dishing does not occur much. Oxidizing agents and oxidation promoters may not be clearly distinguished in their action, and both contribute to oxidizing the surface of the tungsten layer.
選択比向上剤は、タングステンの研磨率とシリコン酸化膜の研磨率との割合、すなわち、研磨選択比を大きくするのに寄与する。特に、シリコン酸化膜の研磨率を下げて研磨選択比を増大させるように作用する。選択比向上剤は、ポリビニールピロリドン（ｐｏｌｙ ｖｉｎｙｌ ｐｙｒｒｏｌｉｄｏｎｅ：以下、「ＰＶＰ」と称する。）、ビニールピリジン（ｖｉｎｙｌ ｐｙｒｉｄｉｎｅ）及びビニールピロリドン（ｖｉｎｙｌ ｐｙｒｒｏｌｉｄｏｎｅ）よりなる群から選ばれた少なくとも一種を含み、ここでは、主としてＰＶＰを用いる。ＰＶＰの含量は、スラリーの総重量に対して、約０．０５重量％以上約３．０重量％未満であることが好ましい。ＰＶＰの含量が約０．０５重量％よりも低ければ、ディッシングが発生し、ＰＶＰの含量が約３．０重量％以上であれば、タングステン研磨率が低いためＣＭＰ工程を行うことが困難になる。ＰＶＰの含量は、スラリーの総重量に対して、約０．０５重量％〜約１．０重量％であることが好ましく、約０．０５重量％〜約０．１重量％であることがさらに好ましい。ＰＶＰの含量が約０．０５重量％〜約１．０重量％の範囲においてタングステン研磨率が適切であり、約０．０５重量％〜約０．１重量％の範囲において研磨選択比に非常に優れているためディッシングもほとんど発生しない。 The selection ratio improver contributes to increasing the ratio between the polishing rate of tungsten and the polishing rate of the silicon oxide film, that is, the polishing selection ratio. In particular, it acts to lower the polishing rate of the silicon oxide film and increase the polishing selectivity. The selectivity improver includes at least one selected from the group consisting of polyvinyl pyrrolidone (hereinafter referred to as “PVP”), vinyl pyridine, and vinyl pyrrolidone. Then, PVP is mainly used. The PVP content is preferably about 0.05% by weight or more and less than about 3.0% by weight based on the total weight of the slurry. If the PVP content is lower than about 0.05% by weight, dishing occurs, and if the PVP content is about 3.0% by weight or more, it becomes difficult to perform the CMP process because the tungsten polishing rate is low. . The PVP content is preferably about 0.05 wt% to about 1.0 wt%, more preferably about 0.05 wt% to about 0.1 wt%, based on the total weight of the slurry. preferable. A tungsten polishing rate is suitable when the PVP content is in the range of about 0.05 wt% to about 1.0 wt%, and the polishing selectivity is very high in the range of about 0.05 wt% to about 0.1 wt%. Because it is excellent, dishing hardly occurs.
ｐＨ調節剤はスラリーのｐＨを調節するために添加され、硝酸などの酸系統を用い、微量を添加してｐＨを約１〜約４に調節する。 The pH adjusting agent is added to adjust the pH of the slurry, and an acid system such as nitric acid is used, and a minute amount is added to adjust the pH to about 1 to about 4.
上述したような酸化チタンを含むスラリーは、従来のスラリーとは全く異なる研磨メカニズムを示す。以下、研磨メカニズムについて詳細に説明する。 A slurry containing titanium oxide as described above exhibits a polishing mechanism completely different from that of a conventional slurry. Hereinafter, the polishing mechanism will be described in detail.
先ず、従来よりタングステンを研磨する研磨剤としてコロイダルシリカが主として用いられてきており、コロイダルシリカを含有するスラリーを用いてタングステン層を研磨する場合、図３の概念図に示すように、循環研磨が行われることが知られている。すなわち、基板にシリコン酸化膜１１０及びタングステン層１２０を形成し、これを研磨する場合、タングステン層１２０の上部にタングステン酸化膜１３０が形成され、その上にコロイダルシリカ研磨剤２００が接触されて研磨が始まる。このとき、シリカ粒子２００はマイナス電位を帯び、非晶質の球状を呈し、タングステン酸化膜１３０の表面に接触されてタングステン酸化膜１３０を研磨し（図３のａ）、最初の膜厚（Ｈ０−Ｈ１）のタングステン酸化膜１３０が除去されるまで研磨する（図３のｂ）。次いで、露出されたタングステン層１２０の表面に再びタングステン酸化膜１３０が形成され、シリカ粒子２００は再びタングステン酸化膜１３０を研磨し（図３のｃ）、２番目の膜厚（Ｈ１−Ｈ２）のタングステン酸化膜１３０が除去されるまで研磨する（図３のｄ）。このようにタングステン酸化膜１３０が形成され、これを研磨・除去する過程が循環的に繰り返し行われながら、タングステン層１２０が除去される（厚さの変化：Ｈ０→Ｈ１→Ｈ２）過程を経ることになる。なお、タングステン層１２０が除去された後、シリコン酸化膜１１０をさらに研磨する場合にも同様に、球状の非晶質シリカ粒子２００がシリコン酸化膜１１０を研磨し、このとき、研磨粒子２００とシリコン酸化膜１１０の材質がほとんど同様であるため研磨速度が速い。 First, colloidal silica has been mainly used as a polishing agent for polishing tungsten, and when polishing a tungsten layer using a slurry containing colloidal silica, as shown in the conceptual diagram of FIG. It is known to be done. That is, when the silicon oxide film 110 and the tungsten layer 120 are formed on the substrate and polished, the tungsten oxide film 130 is formed on the tungsten layer 120, and the colloidal silica abrasive 200 is brought into contact with the tungsten oxide film 130 for polishing. Begins. At this time, the silica particles 200 have a negative potential, have an amorphous spherical shape, are brought into contact with the surface of the tungsten oxide film 130 and polish the tungsten oxide film 130 (a in FIG. 3), and the initial film thickness (H0). Polishing is performed until the tungsten oxide film 130 of -H1) is removed (FIG. 3B). Next, a tungsten oxide film 130 is formed again on the exposed surface of the tungsten layer 120, and the silica particles 200 polish the tungsten oxide film 130 again (FIG. 3c), and the second film thickness (H1-H2). Polishing is performed until the tungsten oxide film 130 is removed (d in FIG. 3). The tungsten oxide film 130 is formed in this way, and the process of polishing and removing the tungsten oxide film 130 is cyclically repeated, and the tungsten layer 120 is removed (thickness change: H0 → H1 → H2). become. Similarly, when the silicon oxide film 110 is further polished after the tungsten layer 120 is removed, the spherical amorphous silica particles 200 polish the silicon oxide film 110. At this time, the polishing particles 200 and the silicon oxide Since the material of the oxide film 110 is almost the same, the polishing rate is high.
これに対し、本発明実施形態の酸化チタンを含むスラリーは全く異なる過程を経て研磨が行われる。図４の概念図を参照すれば、基板にシリコン酸化膜１１０及びタングステン層１２０を形成し、ここにスラリーを供給し、ＣＭＰ工程を行う場合、タングステン層１２０の上部にタングステン酸化膜１３０が形成され、酸化チタン研磨剤３００は少なくとも一部がタングステン酸化膜１３０の内部に浸透してタングステン層１２０及びタングステン酸化膜１３０を研磨する。酸化チタン研磨粒子３００は酸性ｐＨ領域においてプラス電位を帯び、結晶質の多面体状を呈し、スラリーに分散剤が含有されており、酸性ｐＨ領域においてタングステン酸化膜１３０はマイナス電位を帯びる。このため、プラス電位を帯び、結晶面を有する粒子である酸化チタン研磨粒子３００がマイナス電位を帯び、相対的に軟質（約５〜６）であるタングステン酸化膜１３０の内部に食い込んで、一部はタングステン層１２０と直接的に接触し、この状態で研磨が行われ始める。研磨が行われながらタングステン酸化膜１３０及びタングステン層１２０の一部が削り取られ、タングステン酸化膜１３０とタングステン層１２０との間の界面においては再びタングステン酸化膜１３０が形成される。このため、研磨過程が行われる間にタングステン酸化膜１３０は所定の厚さ（ΔＨ）に保たれる。このとき、タングステン酸化膜１３０は略数〜数十Åの範囲に保たれる。また、酸化チタン研磨粒子３００は結晶性を有して硬く、接触面積が広いため化学的な作用よりは機械的な研磨作用の方がさらに強いため、研磨速度が非常に速い。このような研磨過程はタングステン層１２０が除去されるまで行われ続ける。なお、タングステン層１２０が除去された後、シリコン酸化膜１１０をさらに研磨する場合、結晶質の酸化チタン研磨粒子３００がシリコン酸化膜１１０を研磨し、このとき、酸化チタン研磨粒子３００はシリコン酸化膜１１０よりも硬さが低いためコロイダルシリカに比べて研磨が低速で行われる。すなわち、酸化チタン研磨粒子は硬さが約５．５〜約６．５であるのに対し、シリコン酸化膜１１０は硬さが約６〜約７であるため、酸化チタン研磨粒子を用いてシリコン酸化膜を研磨するときに研磨能が減少される。このような研磨能の減少は、シリコン酸化膜が過剰に研磨されて発生するエロージョン現象の減少につながる。 On the other hand, the slurry containing titanium oxide according to the embodiment of the present invention is polished through completely different processes. Referring to the conceptual diagram of FIG. 4, when a silicon oxide film 110 and a tungsten layer 120 are formed on a substrate, and slurry is supplied to the CMP process, a tungsten oxide film 130 is formed on the tungsten layer 120. At least a part of the titanium oxide abrasive 300 penetrates into the tungsten oxide film 130 to polish the tungsten layer 120 and the tungsten oxide film 130. The titanium oxide abrasive particles 300 have a positive potential in the acidic pH region, have a crystalline polyhedral shape, contain a dispersant in the slurry, and the tungsten oxide film 130 has a negative potential in the acidic pH region. For this reason, the titanium oxide abrasive particles 300, which are particles having a positive potential and having crystal faces, have a negative potential and bite into the tungsten oxide film 130 which is relatively soft (about 5 to 6). Is in direct contact with the tungsten layer 120 and polishing begins in this state. Part of the tungsten oxide film 130 and the tungsten layer 120 is scraped off while being polished, and the tungsten oxide film 130 is formed again at the interface between the tungsten oxide film 130 and the tungsten layer 120. Therefore, the tungsten oxide film 130 is kept at a predetermined thickness (ΔH) during the polishing process. At this time, the tungsten oxide film 130 is kept in a range of approximately several to several tens of kilometers. Further, since the titanium oxide abrasive particles 300 are crystalline and hard and have a large contact area, the mechanical polishing action is stronger than the chemical action, so that the polishing rate is very high. Such a polishing process continues until the tungsten layer 120 is removed. When the silicon oxide film 110 is further polished after the tungsten layer 120 is removed, the crystalline titanium oxide polishing particles 300 polish the silicon oxide film 110. At this time, the titanium oxide polishing particles 300 are converted into the silicon oxide film. Since the hardness is lower than 110, polishing is performed at a lower speed than colloidal silica. That is, the hardness of the titanium oxide abrasive particles is about 5.5 to about 6.5, whereas the silicon oxide film 110 is about 6 to about 7 in hardness. The polishing ability is reduced when polishing the oxide film. Such a decrease in polishing ability leads to a decrease in the erosion phenomenon that occurs when the silicon oxide film is excessively polished.
以下、従来のコロイダルシリカ研磨剤と酸化チタン研磨剤を用いて同じ条件のスラリーを製造し、タングステン層とシリコン酸化膜を研磨した結果について説明する。 Hereinafter, the result of manufacturing a slurry of the same conditions using a conventional colloidal silica abrasive and a titanium oxide abrasive and polishing the tungsten layer and the silicon oxide film will be described.
比較例のスラリーは約１重量％のコロイダルシリカ、約０．１重量％の硝酸鉄及び約２重量％の過酸化水素水を含むように製造され、実施例１のスラリーは約１重量％の酸化チタン、約０．１重量％の硝酸鉄及び約２重量％の過酸化水素水を含むように製造され、実施例２のスラリーは約１重量％の酸化チタン、約０．１重量％の硝酸鉄、約２重量％の過酸化水素水及び約０．０５重量％のＰＶＰを含むように製造された。 The comparative slurry was prepared to contain about 1 wt.% Colloidal silica, about 0.1 wt.% Iron nitrate and about 2 wt.% Hydrogen peroxide, and the slurry of Example 1 was about 1 wt.%. Produced to contain titanium oxide, about 0.1 wt% iron nitrate and about 2 wt% hydrogen peroxide, the slurry of Example 2 was about 1 wt% titanium oxide, about 0.1 wt% It was prepared to contain iron nitrate, about 2 wt% aqueous hydrogen peroxide and about 0.05 wt% PVP.
研磨を行うための対象物としては、シリコンウェーハの上に絶縁膜であるシリコン酸化膜と窒化チタンを約１０００Åずつそれぞれ蒸着した後、約６０００Åの厚さにタングステンを蒸着したタングステンウェーハ及びＴＥＯＳ（ｔｅｔｒａｅｔｈｌｙ ｏｒｔｈｏｓｉｌｉｃａｔｅ）を原料として用い、プラズマ蒸着方法を用いて、ウェーハの上にシリコン酸化膜（以下、ＰＥＴＥＯＳと称する。）を約７０００Åの厚さに蒸着したシリコン酸化膜ウェーハを用いた。研磨装備としては、Ｇ＆Ｐテック社製のｐｏｌｉ−７６２装備を用い、研磨パッドとしては、ローム・アンド・ハース社製のＩＣ １０００／ＳｕｂａＩＶ ＣＭＰパッドを用いた。 As a target for polishing, a silicon oxide film and a titanium nitride as an insulating film are deposited on a silicon wafer by about 1000 mm each, and then tungsten is deposited to a thickness of about 6000 mm and TEOS (tetraethly). The silicon oxide film wafer in which a silicon oxide film (hereinafter referred to as PETEOS) was deposited on the wafer to a thickness of about 7000 mm was used by using a plasma vapor deposition method. As the polishing equipment, POLI-762 equipment manufactured by G & P Tech was used, and as the polishing pad, IC 1000 / SubaIV CMP pad manufactured by Rohm and Haas was used.
研磨条件は、下記の通りである。
下降圧力：５ｐｓｉ、
定盤の速度：約９３ｒｐｍ、
スピンドルの速度：約８７ｒｐｍ、
スラリーの流速：約１００ｍＬ／分
The polishing conditions are as follows.
Down pressure: 5 psi
Surface plate speed: approx. 93 rpm
Spindle speed: about 87rpm,
Slurry flow rate: about 100 mL / min
なお、タングステン及びシリコン酸化膜を両方とも約６０秒ずつ研磨した。下記表１に各研磨剤の条件及び研磨結果を示す。 Both tungsten and silicon oxide films were polished for about 60 seconds. Table 1 below shows the conditions of each abrasive and the polishing results.
また、図５は、比較例及び実施例のスラリーを用いて研磨する場合における、基板の各位置別の研磨前後のタングステン層の厚さ及び研磨率を示すグラフである。 FIG. 5 is a graph showing the thickness and polishing rate of the tungsten layer before and after polishing for each position of the substrate when polishing using the slurry of the comparative example and the example.
前記表１及び図５に示すように、コロイダルシリカを研磨剤として用いた従来例に比べて、酸化チタンを研磨剤として用いた実施例はタングステン膜の研磨率が顕著に向上され、これに対し、シリコン酸化膜の研磨率は減少される。このため、タングステンとシリコン酸化膜の研磨選択比が増大される。選択比向上剤を追加した実施例２においてはシリコン酸化膜の研磨率がさらに減少されてタングステンとシリコン酸化膜の選択比がなお一層増大される。なお、コロイダルシリカを研磨剤として用いた従来例の場合、対象物の位置別に研磨厚さに相違があるため研磨均一度（約７％）がよくないが（図５のａ）、酸化チタンを研磨剤として用いた実施例は対象物の位置別に研磨厚さの相違が減少し、研磨均一度が向上され（図５のｂ、ｃ）、特に、選択比向上剤を追加した実施例２においては研磨均一度が約１．５％さらに向上された。 As shown in Table 1 and FIG. 5, in comparison with the conventional example using colloidal silica as the abrasive, the example using titanium oxide as the abrasive significantly improved the polishing rate of the tungsten film. The polishing rate of the silicon oxide film is reduced. For this reason, the polishing selection ratio of tungsten and silicon oxide film is increased. In Example 2 in which the selectivity improver is added, the polishing rate of the silicon oxide film is further reduced, and the selectivity ratio between tungsten and the silicon oxide film is further increased. In the case of the conventional example using colloidal silica as an abrasive, the polishing uniformity (about 7%) is not good because there is a difference in polishing thickness depending on the position of the object (a in FIG. 5). In the embodiment used as the abrasive, the difference in the polishing thickness is reduced depending on the position of the object, and the polishing uniformity is improved (b and c in FIG. 5). The polishing uniformity was further improved by about 1.5%.
一方、基板の上にトレンチなどのパターンが形成された場合にも、研磨工程を行って評価した。先ず、研磨対象物としてパターンが形成された基板を用意する。図６に示すように、シリコン基板１００に絶縁膜としてのシリコン酸化膜１１０を形成し、シリコン酸化膜１１０にトレンチ１１１を設け、その上の全面の上に窒化チタン膜１２１及びタングステン膜１２０を形成する。例えば、図８の走査電子顕微鏡を用いて撮影した断面写真から明らかなように、シリコンウェーハの上にシリコン酸化膜としてのＰＥＴＥＯＳ膜を製造し、そこにパターン幅と長さがそれぞれ約９０ｎｍ、約１９０〜２２０ｎｍであるトレンチを形成し、トレンチを含む全面の上に窒化チタン膜を約２００Åの厚さに蒸着した後、約３０００Åの厚さのタングステン膜を蒸着したウェーハを用いた。研磨装備及び条件は、上述した通りである。 On the other hand, when a pattern such as a trench was formed on the substrate, the polishing process was performed for evaluation. First, a substrate on which a pattern is formed is prepared as an object to be polished. As shown in FIG. 6, a silicon oxide film 110 as an insulating film is formed on a silicon substrate 100, a trench 111 is provided in the silicon oxide film 110, and a titanium nitride film 121 and a tungsten film 120 are formed on the entire surface thereof. To do. For example, as is apparent from the cross-sectional photograph taken using the scanning electron microscope of FIG. 8, a PETEOS film as a silicon oxide film is manufactured on a silicon wafer, and the pattern width and length are about 90 nm and about respectively. A trench having a thickness of 190 to 220 nm was formed, a titanium nitride film was deposited on the entire surface including the trench to a thickness of about 200 mm, and then a tungsten film having a thickness of about 3000 mm was deposited. The polishing equipment and conditions are as described above.
パターンが形成された基板を研磨する場合、研磨が行われながらタングステン膜及びシリコン酸化膜のうちの少なくとも一方が過剰に研磨されてディッシングまたはエロージョンが発生することがある。ここで、図７のディッシング及びエロージョン現象を説明する概念図を参照すれば、ディッシングは、研磨工程後にタングステンパターンの内側が過剰に研磨されて凹む現象、すなわち、トレンチ内のタングステン膜１２０が過剰に研磨されて凹む現象を意味する（図７のＤ）。エロージョンは、金属領域と金属が形成されていない絶縁膜領域との間の段差発生の度合い、すなわち、初期絶縁膜（点線位置）から絶縁膜が過剰に研磨された度合いを意味する（図７のＥ）。 When polishing a substrate on which a pattern is formed, dishing or erosion may occur due to excessive polishing of at least one of the tungsten film and the silicon oxide film while polishing is performed. Here, referring to the conceptual diagram illustrating the dishing and erosion phenomenon of FIG. 7, the dishing is a phenomenon in which the inside of the tungsten pattern is excessively polished and recessed after the polishing process, that is, the tungsten film 120 in the trench is excessive. It means a phenomenon of being polished and recessed (D in FIG. 7). Erosion means the degree of occurrence of a step between the metal region and the insulating film region where no metal is formed, that is, the degree of excessive polishing of the insulating film from the initial insulating film (dotted line position) (FIG. 7). E).
上述したようにして製造された比較例及び実施例１、２のスラリーを用いて図８のトレンチパターンの上にタングステン膜が蒸着されたウェーハを研磨し、その結果を図９〜図１２に示す。図９は、それぞれのスラリーを用いてパターンが形成された基板を研磨した後に評価して、このときに現れたディッシングとエロージョンの量を示すグラフであり、図１０〜図１２は、比較例及び実施例１、２のスラリーを用いてパターンが形成された基板を研磨し、その断面を走査電子顕微鏡（ＳＥＭ）を用いて観察した写真である。ここで、各スラリーを用いる場合、ディッシングとエロージョンの発生の度合い及びその関連性を調べるために、エロージョンが意図的に発生されるまで過研磨を行った。 A wafer having a tungsten film deposited on the trench pattern of FIG. 8 is polished using the slurry of Comparative Example and Examples 1 and 2 manufactured as described above, and the results are shown in FIGS. . FIG. 9 is a graph showing the amount of dishing and erosion which was evaluated after polishing a substrate on which a pattern was formed using each slurry, and FIGS. It is the photograph which grind | polished the board | substrate with which the pattern was formed using the slurry of Example 1, 2, and observed the cross section using the scanning electron microscope (SEM). Here, when each slurry was used, overpolishing was performed until erosion was intentionally generated in order to examine the degree of occurrence of dishing and erosion and the relationship between them.
先ず、あらゆる場合、エロージョンがほとんど発生しないように弱く研磨すれば、ディッシングの発生があまりなかった。但し、コロイダルシリカ研磨剤を用いる比較例の場合には、実施例よりも顕著にディッシングが多く発生した。次いで、研磨時間を長くしてエロージョンを意図的に発生させる場合、図９及び図１０に示すように、比較例においては、エロージョンの量が増大されるにつれて、ディッシングの量が急増する傾向にあった。これに対し、図９、図１１及び図１２に示すように、酸化チタン研磨剤を用いた実施例の場合、エロージョンが約３００Åまではディッシングの量は約６０Åまでであり、それ以上エロージョンが増大されてもディッシングの量は約１００Åと少なかった。特に、選択比向上剤としてのＰＶＰを添加した実施例２の場合、エロージョンが増大してもディッシングはほとんど発生しないことを確認した。 First, in all cases, dishing did not occur much if the surface was polished weakly so that erosion hardly occurred. However, in the case of the comparative example using the colloidal silica abrasive, significantly more dishing occurred than in the examples. Next, when the erosion is intentionally generated by extending the polishing time, as shown in FIGS. 9 and 10, in the comparative example, the amount of dishing tends to increase rapidly as the amount of erosion increases. It was. On the other hand, as shown in FIGS. 9, 11 and 12, in the case of using the titanium oxide abrasive, the amount of dishing is up to about 60 mm when the erosion is about 300 mm, and the erosion is further increased. Even so, the amount of dishing was as small as about 100 mm. In particular, in the case of Example 2 in which PVP as a selection ratio improver was added, it was confirmed that dishing hardly occurred even when erosion increased.
結果的に、コロイダルシリカ研磨剤を用いる場合よりも、酸化チタン研磨剤を用いる場合の方が研磨率やエッチング選択比の側面において優れており、且つ、パターン基板の研磨評価においても優秀性を確認した。ここに選択比向上剤としてのＰＶＰを添加する場合に研磨率はやや下がるが、エッチング選択比に非常に優れており、且つ、パターン基板の研磨評価においてディッシングなどの欠陥がほとんど現れないことを確認することができた。 As a result, the use of titanium oxide abrasives is superior in terms of polishing rate and etching selectivity compared to the case of using colloidal silica abrasives, and the superiority is also confirmed in the polishing evaluation of patterned substrates. did. When adding PVP as a selectivity improver here, the polishing rate is slightly lowered, but it is confirmed that the etching selectivity is very good and that defects such as dishing do not appear in the polishing evaluation of the pattern substrate. We were able to.
上記のスラリーの製造過程は、通常のスラリーの製造過程とは大差ないため、ここでは簡単に説明する。先ず、スラリーを製造する容器を用意し、容器に所望の状態に制御された酸化チタン研磨粒子を所望の量だけ投入する。次いで、容器に超純水を投入して酸化チタン研磨粒子を超純水に分散する。次いで、硝酸鉄を溶解させた超純水溶液を前記容器に所望の量だけ投入して均一に混合する。次いで、硝酸などのｐＨ調節剤を容器に投入し且つ混合して１次スラリーを完成する。過酸化水素水と選択比向上剤は別途の容器に用意し、研磨時に１次スラリーとともに研磨対象物の上に供給する。このとき、過酸化水素水及び選択比向上剤の量を調節して供給してもよい。 Since the above-described slurry manufacturing process is not very different from a normal slurry manufacturing process, it will be briefly described here. First, a container for producing a slurry is prepared, and a desired amount of titanium oxide abrasive particles controlled in a desired state is charged into the container. Next, ultrapure water is charged into the container to disperse the titanium oxide abrasive particles in the ultrapure water. Next, a desired amount of ultrapure aqueous solution in which iron nitrate is dissolved is put into the container and mixed uniformly. Next, a pH adjusting agent such as nitric acid is charged into the container and mixed to complete the primary slurry. The hydrogen peroxide solution and the selective ratio improver are prepared in a separate container and supplied onto the object to be polished together with the primary slurry during polishing. At this time, the amount of the hydrogen peroxide solution and the selection ratio improver may be adjusted and supplied.
以下、本発明の実施形態のスラリーの各成分の含量を変化させ、これを用いてタングステン膜及びシリコン酸化膜を研磨した場合について説明する。 Hereinafter, the case where the content of each component of the slurry of the embodiment of the present invention is changed and the tungsten film and the silicon oxide film are polished using the content will be described.
＜酸化チタンの含量変化＞
上述した方法を用いて酸化チタン研磨粒子の含量を変化させながらスラリーを製造し、これを用いて研磨を行い、その結果を下記表２に示す。このとき、スラリーの総重量に対して、硝酸鉄は約０．１重量％にし、且つ、過酸化水素水は約２重量％にした。研磨装備及び条件は、上述した通りである。
<Change in titanium oxide content>
A slurry was produced using the above-described method while changing the content of titanium oxide abrasive particles, and polishing was performed using the slurry. The results are shown in Table 2 below. At this time, iron nitrate was made about 0.1% by weight and hydrogen peroxide solution was made about 2% by weight with respect to the total weight of the slurry. The polishing equipment and conditions are as described above.
下記表２に示すように、酸化チタン研磨粒子の含量は、スラリーの総重量に対して、約０．２重量％超え約１０重量％以下であることが好ましい。酸化チタン研磨粒子の含量が約０．２重量％以下であれば、タングステン研磨率が約２４９．５Å／分以下と低過ぎてタングステンが研磨し難く、タングステン研磨率が約１０重量％よりも高ければ、固形の含量が増大されるため粒子の分散安定性に問題が発生し、二次粒子の粒径が過剰に大きくなるという問題が発生する。酸化チタン研磨粒子の含量は、スラリーの総重量に対して、約０．７重量％〜５重量％であることが好ましく、約１．０重量％〜約２．０重量％であることがさらに好ましい。酸化チタン研磨粒子の含量が約０．７重量％〜約５重量％の範囲においてはタングステン研磨率が約２５００Å／分以上と優れており、分散安定性が確保される。また、これは、酸化チタン研磨粒子の含量が約１．０重量％〜約２．０重量％の範囲においてはタングステン研磨率が約３７００Å／分〜約３８００Å／分に保たれて非常に優れた研磨率を示し、且つ、安定したＣＭＰ工程を行うことが可能であるためである。 As shown in Table 2 below, the content of titanium oxide abrasive particles is preferably more than about 0.2 wt% and about 10 wt% or less based on the total weight of the slurry. If the content of titanium oxide abrasive particles is about 0.2% by weight or less, the tungsten polishing rate is too low, about 249.5 kg / min., Making tungsten difficult to polish, and the tungsten polishing rate should be higher than about 10% by weight. For example, since the solid content is increased, a problem occurs in the dispersion stability of the particles, and the particle size of the secondary particles becomes excessively large. The content of titanium oxide abrasive particles is preferably about 0.7 wt% to 5 wt%, more preferably about 1.0 wt% to about 2.0 wt%, based on the total weight of the slurry. preferable. When the content of titanium oxide abrasive particles is in the range of about 0.7 wt% to about 5 wt%, the tungsten polishing rate is excellent at about 2500 kg / min or more, and dispersion stability is ensured. In addition, when the content of titanium oxide abrasive particles is in the range of about 1.0 wt% to about 2.0 wt%, the tungsten polishing rate is kept at about 3700 kg / min to about 3800 kg / min, which is very excellent. This is because the polishing rate is shown and a stable CMP process can be performed.
＜過酸化水素水の含量変化＞
上述した方法を用いて酸化剤として働く過酸化水素水の含量を変化させながらタングステン及びシリコン酸化膜の研磨を行い、その結果を下記表３に示す。このとき、スラリーの総重量に対して、酸化チタンの含量は約１．０重量％にし、硝酸鉄は約０．１重量％にした。研磨装備及び条件は、上述した通りである。
<Change in hydrogen peroxide content>
The tungsten and silicon oxide films were polished using the above-described method while changing the content of the hydrogen peroxide solution acting as an oxidizing agent, and the results are shown in Table 3 below. At this time, the content of titanium oxide was about 1.0% by weight and the amount of iron nitrate was about 0.1% by weight with respect to the total weight of the slurry. The polishing equipment and conditions are as described above.
下記表３に示すように、過酸化水素水の含量は、スラリーの総重量に対して、約０．５重量％以上約５．０重量％未満であることが好ましい。過酸化水素水の含量が約０．５重量％よりも低ければ、タングステン研磨率が低過ぎてタングステンの研磨工程を行うことが困難になる。例えば、過酸化水素水が用いられない場合にもタングステン研磨を行うことは可能であるが、研磨率が約１８２．８Å／分と低過ぎて生産性を確保することが困難である。過酸化水素水の含量が約５．０重量％以上であれば、バブルが発生し始める。すなわち、過酸化水素水の含量が約５．０重量％である場合に研磨率は約５８２６．４Å／分と非常に優れているが、硝酸鉄と激しく反応してバブリングが始まることが観察された。過酸化水素水の含量は、スラリーの総重量に対して、約０．５重量％〜約２．０重量％であることが好ましく、約１重量％〜約２重量％であることがさらに好ましい。これは、過酸化水素水の含量が約０．５重量％〜約２．０重量％の範囲においてタングステン研磨率が約１３００Å／分〜約３７００Å／分と適切であり、過酸化水素水の含量が約１重量％〜約２重量％の範囲において最適な濃度を有し、ディッシングがあまり発生しないためである。 As shown in Table 3 below, the content of the hydrogen peroxide solution is preferably about 0.5 wt% or more and less than about 5.0 wt% with respect to the total weight of the slurry. If the content of the hydrogen peroxide solution is lower than about 0.5% by weight, the tungsten polishing rate is too low and it becomes difficult to perform the tungsten polishing step. For example, tungsten polishing can be performed even when hydrogen peroxide solution is not used, but it is difficult to ensure productivity because the polishing rate is too low at about 182.8 Å / min. If the content of the hydrogen peroxide solution is about 5.0% by weight or more, bubbles start to be generated. That is, when the content of hydrogen peroxide is about 5.0% by weight, the polishing rate is very good at about 5826.4 kg / min, but it is observed that bubbling starts by reacting violently with iron nitrate. It was. The content of the hydrogen peroxide solution is preferably about 0.5 wt% to about 2.0 wt%, more preferably about 1 wt% to about 2 wt%, based on the total weight of the slurry. . This is because when the content of hydrogen peroxide is in the range of about 0.5 wt% to about 2.0 wt%, the tungsten polishing rate is appropriate from about 1300 kg / min to about 3700 kg / min. In the range of about 1 wt% to about 2 wt%, and dishing does not occur much.
＜硝酸鉄の含量変化＞
上述した方法を用いて酸化促進剤として働く硝酸鉄の含量を変化させながらタングステン及びシリコン酸化膜の研磨を行い、その結果を下記表４に示す。このとき、スラリーの総重量に対して、酸化チタンの含量は約１．０重量％にし、過酸化水素水の含量は約２重量％にした。研磨装備及び条件は、上述した通りである。
<Change in iron nitrate content>
The tungsten and silicon oxide films were polished using the above-described method while changing the content of iron nitrate acting as an oxidation accelerator, and the results are shown in Table 4 below. At this time, the content of titanium oxide was about 1.0% by weight and the content of hydrogen peroxide water was about 2% by weight with respect to the total weight of the slurry. The polishing equipment and conditions are as described above.
下記表４に示すように、硝酸鉄の含量は、スラリーの総重量に対して、約０．００２重量％以上約０．１重量％以下であることが好ましい。硝酸鉄の含量が約０．００２重量％よりも低ければ、タングステン研磨率が低過ぎてタングステンＣＭＰ工程を行うことが困難である。例えば、硝酸鉄が用いられない場合にもタングステン研磨を行うことは可能であるが、研磨率が約１６３．９Å／分と低過ぎて生産性を確保することが困難である。硝酸鉄の含量が約０．１重量％よりも高ければ、研磨パッドが変色されるという問題が発生する。また、硝酸鉄の含量は、スラリーの総重量に対して、約０．０１重量％〜約０．１重量％であることが好ましく、約０．０５重量％〜約０．１重量％であることがさらに好ましい。これは、硝酸鉄の含量が約０．０１重量％〜約０．１重量％の範囲においてタングステン研磨率が約２７００Å／分〜約３７００Å／分と優れており、硝酸鉄の含量が約０．０５重量％〜約０．１重量％の範囲において最適な濃度を有し、ディッシングがあまり発生しないためである。 As shown in Table 4 below, the iron nitrate content is preferably about 0.002 wt% or more and about 0.1 wt% or less based on the total weight of the slurry. If the iron nitrate content is lower than about 0.002% by weight, the tungsten polishing rate is too low to perform the tungsten CMP process. For example, it is possible to perform tungsten polishing even when iron nitrate is not used, but it is difficult to secure productivity because the polishing rate is too low at about 163.9 mm / min. If the iron nitrate content is higher than about 0.1% by weight, the problem arises that the polishing pad is discolored. Further, the content of iron nitrate is preferably about 0.01 wt% to about 0.1 wt%, and about 0.05 wt% to about 0.1 wt%, based on the total weight of the slurry. More preferably. This is an excellent tungsten polishing rate of about 2700 Å / min to about 3700 Å / min when the iron nitrate content is in the range of about 0.01 wt% to about 0.1 wt%, and the iron nitrate content is about 0.000. This is because it has an optimum concentration in the range of 05 wt% to about 0.1 wt%, and dishing does not occur much.
＜ＰＶＰの含量変化＞
上述した方法を用いて酸化促進剤として働くＰＶＰの含量を変化させながらタングステン及びシリコン酸化膜の研磨を行い、その結果を下記表５に示す。このとき、スラリーの総重量に対して、酸化チタンの含量は約１．０重量％にし、過酸化水素水の含量は約２重量％にし、硝酸鉄の含量は約０．１重量％にした。研磨装備及び条件は、上述した通りである。
<Change in PVP content>
The tungsten and silicon oxide films were polished using the above-described method while changing the content of PVP acting as an oxidation accelerator, and the results are shown in Table 5 below. At this time, the content of titanium oxide was about 1.0% by weight, the content of hydrogen peroxide water was about 2% by weight, and the content of iron nitrate was about 0.1% by weight with respect to the total weight of the slurry. . The polishing equipment and conditions are as described above.
下記表５に示すように、ＰＶＰの含量は、スラリーの総重量に対して、約０．０５重量％以上約３．０重量％未満であることが好ましい。ＰＶＰの含量が約０．０５重量％よりも低ければ、ディッシングが多く発生し、ＰＶＰの含量が約３．０重量％以上であれば、タングステン研磨率が約１５３Å／分と非常に低くてＣＭＰ工程を行うことが困難になる。ＰＶＰの含量は、スラリーの総重量に対して、約０．０５重量％〜約１．０重量％であることが好ましく、約０．０５重量％〜約０．１重量％であることがさらに好ましい。これは、ＰＶＰの含量が約０．０５重量％〜約１．０重量％の範囲においてタングステン研磨率が約１４００Å／分〜約２８００Å／分と適切であり、研磨選択比に優れており、ＰＶＰの含量が約０．０５重量％〜約０．１重量％の範囲において研磨選択比が約５００以上と非常に優れており、ディッシングもほとんど発生しないためである。 As shown in Table 5 below, the PVP content is preferably about 0.05 wt% or more and less than about 3.0 wt% with respect to the total weight of the slurry. If the PVP content is lower than about 0.05% by weight, a large amount of dishing occurs. If the PVP content is about 3.0% by weight or more, the tungsten polishing rate is as low as about 153 kg / min. It becomes difficult to perform the process. The PVP content is preferably about 0.05 wt% to about 1.0 wt%, more preferably about 0.05 wt% to about 0.1 wt%, based on the total weight of the slurry. preferable. This is because when the PVP content is in the range of about 0.05 wt% to about 1.0 wt%, the tungsten polishing rate is appropriate from about 1400 kg / min to about 2800 kg / min, and the polishing selection ratio is excellent. This is because the polishing selection ratio is as excellent as about 500 or more in the range of about 0.05 wt% to about 0.1 wt%, and dishing hardly occurs.
以上、本発明について上述した実施形態及び添付図面に基づいて説明したが、本発明はこれに何ら限定されるものではなく、後述する特許請求の範囲によって限定される。よって、この技術分野における通常の知識を有する者であれば、後述する特許請求の範囲の技術的思想を逸脱しない範囲内において本発明が種々に変形及び修正可能であるということが分かる。 As mentioned above, although this invention was demonstrated based on embodiment mentioned above and attached drawing, this invention is not limited to this at all, and is limited by the claim which is mentioned later. Therefore, those who have ordinary knowledge in this technical field can understand that the present invention can be variously modified and modified without departing from the technical idea of the claims to be described later.
１００：基板
１１０：シリコン酸化膜
１２０：タングステン層
３００：研磨粒子
100: substrate
110: Silicon oxide film 120: Tungsten layer
300: Abrasive particles
Claims (16)
研磨を行う研磨剤及び酸化物形成を促す酸化促進剤を含み、
前記研磨剤として酸化チタン粒子を含み、
前記酸化チタンの含量は、スラリーの総重量に対して、１．０〜２．０重量％であり、
前記酸化チタン粒子は、アナターゼ相とルチル相を有し、前記アナターゼ相とルチル相の総和を１００としたとき、前記アナターゼ相が５０を超え、
前記タングステンの研磨率が３７００Å／ｍｉｎ〜３８００Å／ｍｉｎである、スラリー。 A slurry for tungsten polishing,
A polishing agent for polishing and an oxidation accelerator for promoting oxide formation;
Containing titanium oxide particles as the abrasive,
The titanium oxide content is 1.0 to 2.0% by weight based on the total weight of the slurry,
The titanium oxide particles have an anatase phase and a rutile phase, and when the sum of the anatase phase and the rutile phase is 100, the anatase phase exceeds 50 ,
A slurry in which the polishing rate of tungsten is 3700 Å / min to 3800 Å / min .
前記酸化促進剤の含量は、スラリーの総重量に対して、０．００２重量％以上０．１重量％以下である請求項１に記載のスラリー。 The oxidation promoter includes at least one selected from the group consisting of iron nitrate, potassium ferricyanide, iron chloride, iron sulfate, iron fluoride, iron bromide, copper chloride, copper fluoride and copper bromide,
The slurry according to claim 1, wherein the content of the oxidation accelerator is 0.002 wt% or more and 0.1 wt% or less with respect to the total weight of the slurry.
前記酸化剤の含量は、スラリーの総重量に対して、０．５重量％以上５．０重量％未満である請求項２に記載のスラリー。 As oxidizing agents that form oxides, hydrogen peroxide, urea peroxide, ammonium persulfate, ammonium thiosulfate, sodium hypochlorite, sodium periodate, sodium persulfate, potassium iodate, potassium perchlorate and persulfate Including at least one selected from the group consisting of potassium,
The slurry according to claim 2, wherein the content of the oxidizing agent is 0.5 wt% or more and less than 5.0 wt% with respect to the total weight of the slurry.
研磨を行う研磨剤として酸化チタン粒子を含み、
さらに、酸化物形成を促す酸化促進剤と、タングステンと絶縁膜の研磨選択比を増加させるための選択比向上剤とを含み、
前記酸化チタン粒子は結晶相に形成されるとともに、アナターゼ相とルチル相を有し、前記アナターゼ相とルチル相の総和を１００としたとき、前記アナターゼ相が５０を超え、
前記酸化チタンの含量は、スラリーの総重量に対して、０．２重量％超え１０重量％以下であり、
前記酸化チタン粒子は、平均１次粒子径が１０ｎｍ〜１００ｎｍであり、
前記酸化チタンの含量は、スラリーの総重量に対して、１．０〜２．０重量％であり、前記タングステンの研磨率が３７００Å／ｍｉｎ〜３８００Å／ｍｉｎであるスラリー。 A slurry for tungsten polishing,
Contains titanium oxide particles as a polishing agent for polishing,
Furthermore, an oxidation promoter that promotes oxide formation, and a selectivity improver for increasing the polishing selectivity of tungsten and the insulating film,
The titanium oxide particles are formed in a crystalline phase, have an anatase phase and a rutile phase, and when the sum of the anatase phase and the rutile phase is 100, the anatase phase exceeds 50,
The content of the titanium oxide is more than 0.2 wt% and 10 wt% or less with respect to the total weight of the slurry,
The titanium oxide particles have an average primary particle diameter of Ri 10nm~100nm der,
The titanium oxide content is 1.0 to 2.0% by weight based on the total weight of the slurry, and the tungsten polishing rate is 3700 研磨 / min to 3800 Å / min .
The slurry according to claim 15 , wherein the titanium oxide particles have an average primary particle diameter of 15 nm or more and less than 50 nm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120038419A KR101257336B1 (en) | 2012-04-13 | 2012-04-13 | Polishing slurry and method of polishing using the same |
| KR10-2012-0038419 | 2012-04-13 | ||
| PCT/KR2012/007367 WO2013154236A1 (en) | 2012-04-13 | 2012-09-14 | Polishing slurry and method of polishing using the same |
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| Publication Number | Publication Date |
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| JP2015502417A JP2015502417A (en) | 2015-01-22 |
| JP6030145B2 true JP6030145B2 (en) | 2016-11-24 |
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| JP2014539865A Active JP6030145B2 (en) | 2012-04-13 | 2012-09-14 | Polishing slurry and substrate polishing method using the same |
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| US (1) | US20140312266A1 (en) |
| JP (1) | JP6030145B2 (en) |
| KR (1) | KR101257336B1 (en) |
| CN (1) | CN104066807B (en) |
| TW (1) | TWI608061B (en) |
| WO (1) | WO2013154236A1 (en) |
Families Citing this family (9)
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|---|---|---|---|---|
| WO2014109929A1 (en) | 2013-01-11 | 2014-07-17 | Applied Materials, Inc | Chemical mechanical polishing apparatus and methods |
| WO2016032145A1 (en) * | 2014-08-26 | 2016-03-03 | 주식회사 케이씨텍 | Polishing slurry composition |
| CN106661429B (en) * | 2014-08-26 | 2019-07-05 | 凯斯科技股份有限公司 | Polishing slurries composition |
| KR101682097B1 (en) * | 2014-08-26 | 2016-12-02 | 주식회사 케이씨텍 | Polishing slurry composition |
| KR101834418B1 (en) * | 2015-10-02 | 2018-03-05 | 유비머트리얼즈주식회사 | Slurry and substrate polishing method using the same |
| CN107914211A (en) * | 2016-10-11 | 2018-04-17 | 中芯国际集成电路制造(上海)有限公司 | A kind of chemical and mechanical grinding method |
| US10647887B2 (en) * | 2018-01-08 | 2020-05-12 | Cabot Microelectronics Corporation | Tungsten buff polishing compositions with improved topography |
| JP7368997B2 (en) | 2019-09-30 | 2023-10-25 | 株式会社フジミインコーポレーテッド | polishing composition |
| KR102415203B1 (en) * | 2020-08-24 | 2022-06-30 | 에스케이씨솔믹스 주식회사 | Polishing pad and preparing method of semiconductor device using the same |
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| US5340370A (en) * | 1993-11-03 | 1994-08-23 | Intel Corporation | Slurries for chemical mechanical polishing |
| US5993686A (en) * | 1996-06-06 | 1999-11-30 | Cabot Corporation | Fluoride additive containing chemical mechanical polishing slurry and method for use of same |
| JPH10121035A (en) * | 1996-08-30 | 1998-05-12 | Showa Denko Kk | Composition for polishing magnetic disk substrate |
| US6152976A (en) * | 1996-08-30 | 2000-11-28 | Showa Denko Kabushiki Kaisha | Abrasive composition for disc substrate, and process for polishing disc substrate |
| US6068787A (en) * | 1996-11-26 | 2000-05-30 | Cabot Corporation | Composition and slurry useful for metal CMP |
| US6083419A (en) * | 1997-07-28 | 2000-07-04 | Cabot Corporation | Polishing composition including an inhibitor of tungsten etching |
| JP2002528903A (en) * | 1998-10-23 | 2002-09-03 | アーチ・スペシャルティ・ケミカルズ・インコーポレイテッド | Slurry system containing activator solution for chemical mechanical polishing |
| MY128169A (en) * | 1999-06-28 | 2007-01-31 | Showa Denko Kk | Abrasive composition for substrate for magnetic recording disks and process for producing substrate for magnetic recording disk. |
| US6478837B1 (en) * | 1999-06-28 | 2002-11-12 | Showa Denko K.K. | Abrasive composition substrate for magnetic recording disks and process for producing substrates for magnetic recording disk |
| US6280490B1 (en) * | 1999-09-27 | 2001-08-28 | Fujimi America Inc. | Polishing composition and method for producing a memory hard disk |
| KR100710538B1 (en) * | 1999-12-27 | 2007-04-24 | 다이호고교가부시키가이샤 | Hard surface treating agent, stain-proofing agent and method for surface treatment |
| JP2001269859A (en) * | 2000-03-27 | 2001-10-02 | Jsr Corp | Aqueous dispersing element for polishing chemical machine |
| JP2002009023A (en) * | 2000-06-21 | 2002-01-11 | Asahi Kasei Corp | Composition for polishing metal film of semiconductor substrate |
| JP2002003825A (en) * | 2000-06-21 | 2002-01-09 | Asahi Kasei Corp | Optically active composition for polishing semiconductor substrate metal film |
| US6551935B1 (en) * | 2000-08-31 | 2003-04-22 | Micron Technology, Inc. | Slurry for use in polishing semiconductor device conductive structures that include copper and tungsten and polishing methods |
| JP2002173669A (en) * | 2000-12-05 | 2002-06-21 | Asahi Kasei Corp | Slurry for polishing metal film on semiconductor substrate |
| JP4003116B2 (en) * | 2001-11-28 | 2007-11-07 | 株式会社フジミインコーポレーテッド | Polishing composition for magnetic disk substrate and polishing method using the same |
| KR20030063763A (en) * | 2002-01-24 | 2003-07-31 | 한국과학기술연구원 | Slurry for tungsten cmp |
| US7132058B2 (en) * | 2002-01-24 | 2006-11-07 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Tungsten polishing solution |
| US20030139047A1 (en) * | 2002-01-24 | 2003-07-24 | Thomas Terence M. | Metal polishing slurry having a static etch inhibitor and method of formulation |
| US7513920B2 (en) * | 2002-02-11 | 2009-04-07 | Dupont Air Products Nanomaterials Llc | Free radical-forming activator attached to solid and used to enhance CMP formulations |
| TWI288772B (en) * | 2003-01-24 | 2007-10-21 | Rohm & Haas Elect Mat | Tungsten polishing solution |
| KR100600598B1 (en) * | 2003-10-02 | 2006-07-13 | 제일모직주식회사 | Slurry Composition for Chemical Mechanical Polishing of Tungsten Wire |
| US7172493B2 (en) * | 2003-11-24 | 2007-02-06 | Nikon Corporation | Fine force actuator assembly for chemical mechanical polishing apparatuses |
| US20050194562A1 (en) * | 2004-02-23 | 2005-09-08 | Lavoie Raymond L.Jr. | Polishing compositions for controlling metal interconnect removal rate in semiconductor wafers |
| KR20060099313A (en) * | 2005-03-11 | 2006-09-19 | 삼성전자주식회사 | Chemical mechanical polishing slurry containing oxide polishing resistant |
| US20070075042A1 (en) * | 2005-10-05 | 2007-04-05 | Siddiqui Junaid A | Stabilizer-Fenton's reaction metal-vinyl pyridine polymer-surface-modified chemical mechanical planarization composition and associated method |
| US7803711B2 (en) | 2007-09-18 | 2010-09-28 | Cabot Microelectronics Corporation | Low pH barrier slurry based on titanium dioxide |
| CN101724346A (en) * | 2008-10-10 | 2010-06-09 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| JP2011014840A (en) * | 2009-07-06 | 2011-01-20 | Adeka Corp | Polishing composition for cmp |
-
2012
- 2012-04-13 KR KR1020120038419A patent/KR101257336B1/en active IP Right Grant
- 2012-09-14 WO PCT/KR2012/007367 patent/WO2013154236A1/en active Application Filing
- 2012-09-14 JP JP2014539865A patent/JP6030145B2/en active Active
- 2012-09-14 US US14/357,768 patent/US20140312266A1/en not_active Abandoned
- 2012-09-14 CN CN201280065754.4A patent/CN104066807B/en active Active
- 2012-09-21 TW TW101134779A patent/TWI608061B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013154236A8 (en) | 2014-04-03 |
| US20140312266A1 (en) | 2014-10-23 |
| CN104066807B (en) | 2016-06-29 |
| KR101257336B1 (en) | 2013-04-23 |
| JP2015502417A (en) | 2015-01-22 |
| WO2013154236A1 (en) | 2013-10-17 |
| TW201341490A (en) | 2013-10-16 |
| CN104066807A (en) | 2014-09-24 |
| TWI608061B (en) | 2017-12-11 |
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